by EUGENIA KALANTZIS
Department of Civil Engineering and Applied Mechanics McGill University, Montreal May 1997
A THESIS SUBMITTED TO THE FACULTY OF GRADUATE STUDlES AND RESEARCH IN PARTIAL FULFlLLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF ENGINEERING
O Eugenia Kalantzis, 1997
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This report presents the results of a study on the benefit of chlonde ion testing in the prediction of soil comsivity, which is determined using the method of iiiear polarization. Existing indusüy standards such as AWWA Cl05 and PACE 823 are currently being used to evaluate the comsivity of soils. ïhese standards consist of various tests, whose results permit the calculation of a comsivity index. ï h e following tests are suggested: pH, oxidationreduction potential, suifide ion content, resistivity, drainage ability, soil type, and moisture content. Up to this point, no standards have incorporated chloride ion testing into theû testing procedure, even though the effect of chlonde ions on the corrosion rate is well documented. It is the goal of this project to determine whether there is enough evidence to suggest that chlonde ion content be introduced into existing standards.
In total, 153 soils were tested following the AWWA Cl05 and PACE 823
standards, as well as for the chlonde ion content. Of these, 75 soils were tested using linear polarization to determine the "huee' corrosivityof the soils. The analysis results showed that the information provided by the chlonde ion content was not significant enough to suggest that this variable be added to the existing grids. This is due to the fact that soi1 resistivity, which is a required test in both standards, accounts for the presence of chlonde ions. However, it should be noted that the chlonde ion content is a bener predictor of corrosivity than soil resistivity, and it is suggested that chlonde ion content be tested whenever possible.
Ce rapport présente les résultats d'une étude sur la nécessité de déterminer la teneur en chlorures dans I'évaluation de la corrosivité des sols, cene dernière étant obtenue par la méthode de la polarization linéaire. Présentement, les normes utilisées par l'industrie sont basées sur des grilles d'évaluation permettant le calcul d'un index de corrosivité, e.g., les grilles AWWA Cl05 et PACE 823. Chaque g N e d'évaluation est constniite à partir d'une série de tests, notamment le type de sol, le pH, le potentiel rédox, la teneur en sulfures, la résistivité, le drainage, et l'humidité du sol. lusqu'à date, aucune norme n'inwrpore la teneur en chionires dans sa grille d'évaluation, même si l'effet des chlomres sur la vitesse de corrosion est bien documenté. l'objectif de cette étude est donc de déteminer si la teneur en chionire devrait être introduite dans les grilles d'évaluation. Au total, 153 spécimens de sols varies ont été testés selon les grilles AWWA Cl05 et PACE 823, ainsi que pour la teneur en chionires. De ce nombre, 75 ont été testés par la méthode de la polarization linéaire, et la corrosivité de ces sols a été ainsi formellemnt déterminée. Après l'analyse des résultats des tests, il a été determiné que l'information additionnelle fournie par la teneur en chionires n'a pas été significative pour suggérer que ce paramètre soit incorporé dans les grilles existantes. Ceci est dû au fait que la résistivité du sol, qui est une mesure déjà incluse dans les deux normes, représente indirectement sa teneur en chionires. Par contre, il est important de noter que la teneur en chionires est une variable qui prédit mieux la corrosivité du sol que la résistivité. Cependant, il est fortement suggéré que la teneur en chlorures soit évaluée et étudiée si possible.
iii
6.1 and 4 .1.3 2.7.6.5 2.1...1..TABLE OF CONTENTS ABSTRACT ii RÉsm LIST OF FIGURES LIST OF TABLES NOTATION AND ABBREVIATiONS ACKNOWLEDGMENTS 1. viii xi Xlll .2. The Exchange Current Densiîy.1.1.4 2.7 Uniform Attack Galvanic Attack Crevice Corrosion Pitting Corrosion Erosion Corrosion Selective Leaching Stress Corrosion 4 7 7 8 1O 11 11 12 13 14 16 22 23 23 25 27 Why Do Metals Corrode? Deteminhg the Rate of Corrosion .1.1.1 Principles of Electrochemical Corrosion Necessary Elements for Corrosion Physical Foms of Corrosion 2. INTRODUCTION 2.2.1.6 2.2.1 2.2 2.1. xvii 1 4 4 2.1 2..2.2. i Detemination of r.2 2.2. 2. CORROSION AND CORROSION CONTROL 111 .1.2.. Activation Polarization Concentration Polarization Effect of Varying Parameters Using Polarization Diagrams 27 'Concentration PO2 and H .
1 2.4 2.4 3.7. PROCEDURES AND APPARATUS 3.2 2.3.1 3.8.7.3.7 3.5 3.7.3 3.7.2 3.8.3 3.7.4 2.1.1.1 3.1.2 2.2.6 2.4.1.3 2.8 Soil Samples Soil Type Drainage AbilityIMoisture Content pH OxidationReduction Potential (Redox Potential) Resistivity.2 2.1 2.2 3.1.2.6 3.2 2.3.8. p hifide Content Chloride Concentration 3.1 2.3 2.4 2.3 2.5 2.4.2.3.4 Necessary Equipment Sample Preparation Electrode Preparation Preparation of Calibrating Solutions .2 O2 Solubility Multiple Corrodents Galvanic Attack Passivity Chloride Content Measuring Corrosion Rates Tafel Extrapolation Liear Polanzation Differential Aeration Cells Galvanic Anack Selective Leaching StressCorrosion Cracking AWWA Cl05 PACE 823 Soi1 Corrosion and Its Effects on Underground Infrastmcture Standards for Determining Corrosivity of Soils 3.8.
1.5 3.1 Analy~is of Preliminary Data 4.1. ANALYSIS O F EXPERIMENTAL RESULTS AND DISCUSSION 4.9.3.5 3.3 3.1 4.1 5.8.9 3.1.1.2.2 Summary of Results Recommendation for Future Work .7 3.6 4.6 3.8.2.7 4.1 4.10 Calibration of Electrode Calibration C w e and Equation Testing Soil Samples Determination of Concentration of Chloride Ions of Soil Necessary Equipment Trial Runs and Reproducibility of Results Sample Preparation Preparation of the Working Electrode Polarization ofthe Steel Specimen Linear Polanzation Calculatingthe Corrosivity Indices According to AWWA and PACE 4.9.8.9.9.2 3.8.1.1.1.4 4.2 4.9.4 3.3 Data Exploration Transformation of Variables Regression of the Individual Variables Correlation Matrix RSQUARE Results Categoncal Variables Variables Retained For Further Analysis Determiniig Significance The Effect of Removing Outliers Consideration of Chlorides in Predicting the Corrosion Rate Power Analysis 5.1 3.3 4.5 4. CONCLUSIONS AND RECOMMENDATIONS 5.8 3.2 4.2 4.
APPENDM A: DERIVATION OF POTENTIAL EQUATIONS A.l
A.2
Equation for Czn Equation for b c u Equation for b+
A.3
APPENDIX B: TESTING FOR CHLORIDE ION CONCENTRATION B.l Creating a Concentration vs. Potential Curve
APPENDIX C: TRIALS FOR REPRODUCIBILITY APPENDIX D: PRINCIPLES OF REGRESSION ANALYSIS D.l D.2 D.3
D.4 D.5
Data Exploration Simple Linear Regression Analysis Data Transformations Multiple Variable Regression Categorical Variables Outliers Variable Selection Model Validation Power The SAS Statistical Package
D.6 D.7
D.8
D.9 D.10
vii
LIST OF FIGURES
The Two Stages of Crevice Corrosion Pining Corrosion Erosion Corrosion Microstructure of Gray Cast Iron Intercrystalline Crack Transcrystallie Crack Stable and Unstable Positions Schematic of a CdZn Banery
4 vs. log 1 for CdZn Banery
Polarization Diagram for Corrosion in Acidic Solution Polarization Diagram for Corrosion in Neutra1 Aerated Water Dependence of I,,, on the Value of 1, Activation Polarization Diagram Concentration Polarization Diagram Distribution of H 'in Time Effect of Varying PO2 Variation of 0 2 Solubility with NaCl Concentration Effect of Multiple Corrodents Galvanic Anack Polarization Diagram of a Metal Exhibiting Passivity Variation of 1, and 1, with Potential4 Tafel Curve Schematic of Setup for Tafel Test Tafel Curve Obtained by Varying Q Tafel Regions
, , fiom the Tafel C w e Obtaining i
L i e a r Polarization Curve Components of the Working Electrode
Typical Tafel Plot Typical Linear Polarization Curve Spreadsheet for Quick Calculation of Corrosivity Indices
SAS Output: Univariate Procedure using pHdir SAS Output: Univariate Procedure usingpHsat SAS Output: Univariate Procedure using Reddir SAS Output: Univariate Procedure using Reddir,
with Extreme Values Removed
SAS Output: Univariate Procedure using Redsar SAS Output: Univariate Procedure using Redsat,
with Extreme Values Removed
SAS Output: Univariate Procedure using Resdir SAS Output: Univariate Procedure using Ressar SAS Output: Univariate Procedure using Chloride SAS Output: Univariate Procedure using CorrRate SAS Output: Univariate Procedure using LChl SAS Output: Univariate Procedure using LResdir SAS Output: Univariate Procedure using LRessar SAS Output: Univariate Procedure using LCorr SAS Output: Univariate Procedure usingpHdir Residual SAS 0utput:pHdir Residual vs. Predicted Value of CorrRare SAS Output: Univariate Procedure usingpHsat Residual SAS 0utput:pHsat Residual vs. Predicted Value of CorrRaie SAS Output: Univariate Procedure using Reddir Residual SAS Output: Reddir Residual vs. Predicted Value of CorrRoie SAS Output: Univanate Procedure using Redsat Residual SAS Output: Redsat Residual vs. Predicted Value of CorrRate SAS Output: Univanate Procedure using LResdir Residual SAS Output: LResdir Residual vs. Predicted Value of CorrRate SAS Output: Univariate Procedure using LRessat Residual
SAS Output: LRessat Residual vs. Predicted Value of CorrRate SAS Output: Univariate Procedure using LChl Residual SAS Output: LChl Residual vs. Predicted Value of CorrRate SAS Output: Correlation Matrix SAS Output: Correlation Matrix for Clay Samples SAS Output: Correlation Matnx for San6 Samples SAS Output: Correlation Matrix for SandClay Samples Potentials Obtained f?om Calibrating Solutions: Senes 1 Calibration Curve for Senes 1 Trial No. 1: Tafel Results Trial No. 1: Linear Polarization Results Trial No. 2: Tafel Resilts Tnal No. 2: Linear Polarization Results Stem and Leaf Diagram Stem and Leaf Diagrarn and Boxplot Normal Probability Plot
Y vs. X Plot
Example of an Insignificant Predictor ANOVA Table Normal Distribution Normally Distnbuted Y Values
Y Values Not Distributed Normally
Ideal Y vs. X Distribution NonLinear Relationship Between X and Y Venn Diagrams for 1 and 2 Independent Vanables Effect of Outliers on R'
96 Corrosion Rates Corrosion indices According to AWWA Corrosion Rates According to PACE Values of LChl Values of LResdir Values of LRessat Values of LCorr Residual Characteristics: pHdir Residual Characteristics:pHsut .LIST OF TABLES Elecîromotive Senes Galvanic Senes for Seawater Typical p Values Soil Type Results Drainage Ability Results Moisture Content Results pHdirect Results pHsaturated Results Redoxdirect Results Redoxsatwated Results psaturated Results pdirect Results Sulfide Content Results Using lodine Solution Sulfide Content Results Using HCI and Lead Acetate Paper Preparation of Calibrating Solutions Chloride Ion Concentrations Values Specified for Tafel Test Values Specified for Linear Polanzation Test Results Obtained for Soil Sample No.
2. and Power Relationship Between n and Power Values of L for a = 0.3.5 xii .Residual Charactenstics: Reddir Residual Charactenstics: Redrar Residual Characteristics: LResdir Residual Characteristics: LRessat Residual Characteristics: LChl Possible 1.P. and 4Variable Models Possible Models with Corresponding SSE and DOF Values Cntical Values for F Information about Possible Models Correlation Matnx Dummy Variables for Soilfype: 2 Variable Case Dummy Variables for Soilfype: 3 Variable Case Relationship Between a.
NOTATION AND ABBREVIATIONS Type 1error Type II emor Point of intersection of a line with y = O Slope of a line Overvoltage Current density Current density at the anode Current density at the cathode Corrosion current density Exchange current density Mean Resistivity Summation Standard deviation Potential Nerst potential Standard Nerst potential Corrosion potential Oxidation potential Reduction potential Benchmark mode1 in a significance test Model being tested in a significance test Ohm Degrees Celsius Activity Amperes xiii .
ANOVA &x Analysis of Variance Activity of species being oxidized Activity of species &mg reduced Atmosphere American Water Works Association Coulomb Calories Cook's distance Variable representing chloride content of soi1 Centimeter Mallow's number Decade Degrees Degrees of fieedom Correlation coefficient Residual Electron Equivalent Faraday's Constant Effect size Current Corrosion Current Joule Kelvin Number of variables in the Rmode1 Mass transfer coefficient kilogram liters ad atm AWWA C cal CD Chloride cm CorrRare Variable representing the corrosion rate of a metal in a soi1 CP dec deg DOF Drainage Variable representing the drainage ability of a soi1 xiv .
when measured afier saturation with distilled water Variable representing the resistivity of a soil. when measured afier saturation with distilled water Partial pressure of oxygen Parts per million Predicted residual sum of squares Procedure statement in SAS Adjusted partial correlation Variable representing the reduction potential of a soil. when measured as received in the laboratory Variable representing the logarithm ofthe resistivity of a soil. when measured afier saturation with distilled water M mm MU+ Moisture mV N N P pHdir Metal Millimeter Metal ion Variable representing the moisture coptent of a soi1 Millivolt Number of obse~ations Solution normality Number of variables in a mode1 Variable representing the pH of a soil. when measured as received in the laboratory Variable representing the pH of a soil. when measured as received in the laboratory Oxidationreduction Variable representing the reduction potential of a soil. when measured as received in the laboratory PO2 PPm PRESS PROC R2adjurted Reddir Redox Redsat .Variable representing the logarithm of the cliloride concentration of a soi1 Variable representing the logarithm of the corrosion rate of a metal in a soi1 Variable representing the logarithm of the resistivity of a soil.
Y Y' Y=. Dummy variable Independent variable Dependent variable Mean of Y year v VIF wt.Ressat Variable representing the resistivity of a soil. when measured afler saturation with distilled water b Polarization resistance SandIClay A soi1 composed of a mixture of soil and clay particles SAS SSE Siatistical Analysis System Error surn of squares Variable representing the result of the sulfide content test using HCI and Lead Acetate Paper Suljl Variable representing the result of the sulfide content test using the iodine solution SuIfHcr T Temperature Volt Variation Inflation Factor Weight percentage Mean of X. % X' xd x. xvi .
Montreal for the unrestricted access to equipment and materials. Montreal. Furthemore. Saeed M. for suggesting the research topic. without which this project would not have been possible. Mina. Nourrediie Kadourn of COREXCO. whose unending guidance and encouragement proved invaluable in the successhl realization of this research program. and for devoting considerable attention to its progress. Fially. 1 would like to thank my family and fiiends for their support and encouragement. xvii . The research project was supported by the Natural Sciences and Engineering Research Council's PGSA Scholarship held by the author. 1 would iiie to express my gratitude to my supervisor. Prof. Gérard Benchétrit and to COPEXCO. 1 am very grateful to Mr.ACKNOWLEDGMENTS First and foremost. 1 am also deeply indebted to Mr.
.
industnal and fire fighting purposes. The fundamental cause of the detenoration of the pipes is soi1 corro~ionl'~. soil corrosion. The physical integrity of the water distribution system is an essentiel component for the health and economic well being of Canadians. which account for 70% of the water mains. However. natural gas pipelines.CHAPTER 1: INTRODUCTION The corrosion of underground infrastructure is a very widespread problem. and is composed of the test results in combiiation with the appropnate points allocated to each. and to establish a quick and easy method of evaluating the corrosivity of soils. When a nahiral gas pipeline or a gasoline storage container fails. there is a high danger of fire and subsequent explosion. Standards such as that of the American Water Works Association (AWWA C 105) and PACE 823 are widely used to determine whether or not a metal subjected to a given soi1 will suffer detenoration. Certain standards are now in use by the industry to determine the extent to which a soi1 is considered corrosive. as Canadians depend on drinking water for domestic. The majority of the problems occur on water mains made up of cast or ductile iron. ïhere is therefore a great need to determine the causes of soi1 corrosion. the environmental darnage caused by such failures is oflen devastating and irreparable. However. Furthemore. certain soi1 charactenstics are measured and a standard grid allows the technician to calculate a corrosivity index for the soil. The term grid refers to the established method of calculating the corrosivity index. and gasoline storage containers are only some of the many structures affected by soi1 corrosion al1 around the world. Failure of water mains can be equally dismptive. $200 million are spent on renewing iron water mains in Canada. It has been argued that chloride ion content is measured indirectly through the measurement of the soi1 resistivity. Every year. In al1 of these standards. This variable accounts for the total ion content responsible for the conductive nature of the soil. Stmctures such as water mains. There has been much research done in the field of corrosion and. none of the standards take into account the chloride ion content of the soil. in particular. which is incorporated in some f o m in al1 the grids. chlonde .
~.ions have a dual role in the corrosion process. drainage ability. pH. in this project. the variable obtained using the method of linear polarization is considered the "true" corrosion rate of the pipe in the given soil. If the answer is affumative. but they also inhibit passivity of the metal. and chloride ion content. and to outline the limitations and advantages of each standard. and to determine which variables play the most important role in the corrosion O r . For this reason. The objectives of this project are the following: O To study the method of linear polarization (applications and limitations). or a new grid be created to adequately account for the soil chloride ion content. The linear polarization test (an accelerated electrochernical test which can be used to evaluate the corrosion rate) will be used to determine the soil corrosivity. and to determine the extent to which it can be used in the field of soi1 corrosion. The above variables are analyzed using the statistical package SAS. and has recently been used in the investigation of soil corrosion 17]. This method has been used extensively in the examination of steel corrosion in reinforced c~ncrete['. it is suspected that the ineasurement of chloride ion concentration will permit prediction of the corrosivity of a soi1 more accurately than is possible without the knowledge of this parameter. resistivity.~]. They not only promote corrosion because they are conductive by nature. To become familiar with the AWWA and PACE standards for soil testing. sulfide content. and the relationship between the soi1 characteristics and the "true" corrosion rate will enable the analyst to determine the extent to which each soil characteristic predicts the actual corrosion ratels1.e. they inhibit the formation of an oxide layer on the metal surface which protects the metal from corrosion[21. The following soil characteristics are measured: soil type. To study the relationship between the soi1 characteristics and the corrosion rate of the soil.'. i. and it will be compared with the other soi1 characteristics. oxidationreduction potential. It is the main goal of this research program to determine whether the chloride ion concentration can provide the information that the variables already being tested in the standards do not provide. then this variable can be recommended for incorporation into the existing grids.
to suggest that this variable be incorporated into the existing grids or that a new grid be created to include this variable. Finally. and the analysis of the collected data using SAS.process. and the results are discussed. the rnethods and equipment used to rneasure the vanous soi1 characteristics are presented. if so. conclusions and recommendations for future work are made in Chapter 5: Conclusions and Recommendations. The report is divided into two main sections: the rneasurement of the soi1 characteristics. What is the role of the variables which are expected to be the rnost influential? What is the importance of the chlonde ion content of the soi1 in predicting the corrosion rate? To determine whether the chlonde ion concentration provides information that the variables already 'bcing tested in the standards do not provide and. In Chaprer 3: Procedures and Apparatus. The statistical analysis of the experirnental data obtained in Chapter 3 is presented in Chapier 4: Analysis of Erperimental Results. and provides the background information essential to understand the variables being studied and their role in the corrosion process (Chapter 2: Corrosion and Corrosion Tesring). Chapter 2 introduces the basic phenornena underlying the corrosion process. .
undergoes the following reaction: .1 Necessarv elements for corrosion Corrosion can take various forms. A sound knowledge of the basic principles will allow the corrosion engineer to predict the aggressiveness of a given environment. The anode consists of a metal (Fe.7e91. or to choose materials which will not be affected by the existing aggressive environment. along with the information deemed essential to understandiig the variables selected for this study. an electrical conductor. and can occur under different circumstances. and their role in the corrosion process. Cu. and examines the principles underlying the determination of the corrosion rate. there are certain constants in al1 corrosion processes.) which is oxidized in the presence of an oxidizing agent. a cathode. The metal.1 Principles of Electrochernical Corrosion 2. to alter the environment to decrease its corrosivity to a particular material. The following section introduces the causes and effects of soi1 corrosion. The basics of electrochemistry with respect to corrosion of metals in aqueous media are briefly reviewed. and an ionic conductor [2. 2. etc.CHAPTER 2: CORROSION AND CORROSION TESTING To fully understand the factors that conhibute to corrosion in a particular environment.1. Four elements must be present for corrosion to occur: an anode. a thorough howledge of the various corrosion mechanisms is essential. or a corrodent. to protect the materials from corrosion. and the final section discusses the AWWA and PACE standards currently being used by the industry to determine the corrosivity of soils. denoted by M. However. The second section of this report introduces the reader to the method of linear polarization.
1) It is the anode that undergoes damage. the cathode or corrodent is consuming the electrons released by the oxidation of the metal. the complete reaction is as follows: . the complete equation becomes: in an acidic A product of this reaction is hydrogen gas. releasing ions (Mn') and n electrons. rainwater or sea~ater)[~'. the cathode is undergoing reduction. in neutral aerated water.g. and the neutral aerated water (e.3b) +2 O K The complete corrosion equation is obtained by combiniig the equation of the oxidation of metal M with one of the above reduction equations.91. or a solution nch in oxygen or hydrogen ions.M + Mn' +ne' Oxidation of metal M Anodic Reaction (2. While the anode is undergoing oxidation. The metal M dissolves. or hydrogen embrittlement of metals [2. Some examples of metal oxidations are: The cathode can consist of a metal. During reduction. which can often cause problems such as hydrogen blistenng. The reduction equations are as follows: 2H'+2e'+Hz Acid solution: Neutral Aerated Water: 112 0 2 + H?O+ 2 e' Reduction of H ' Reduction of 0 2 (2. The two corrodents that are of major importance are the acidic solution.3a) (2.~]. environment.
then the metal itself is the electrical conductor. then any metal wire connecting the two will act as the electrical conductor through which the eiectrons will move [2. which allows electrons to move fiom the anode. the anode would now be negatively charged due to the presence of the electrons released.7. allows the movement of ions fiom the anode to the cathode thus ensuring electrical neutrality and allowing the corrosion process to continue 12. Furthermore. As the ions move fiom . or when the two sites are located on separate pieces of metal which are in physical and electncal contact with one another. then Fe(OH)2 or m t is precipitated when oxygen is the corrodent.7.91. where they are released. to the cathode. the electrical conductor.91. which is usually the metal itself. which is the aqueous solution in contact with both the anode and the cathode. The anode is the site where damage occurs as the rnetal is oxidized and electrons and ions are released. If this movement of electrons cannot proceed. or a metal wire connecting the two sites.7. Furthemore.n i e term 112 O2 in the above equation refers to the dissolved oxygen present in the water. if the two sites are found on separate pieces of rnetal. The electrolyte. In the case when a piece of metal is the site of both the anodic and cathodic reactions. or the electrolyte. The electrons travel fiom the anode to the cathode via the electrical conductor. i n summary.91. Another element essential for corrosion to occw is an electrical conductor. The cathode is the site where electrons are consumed while oxygen or hydrogen are reduced.91. the cathode. where they are consumed [2. the f o u essential elements to the corrosion process are the anode. and this disequilibnum would stop any further oxidation and release of electrons [2. The last essential element in the corrosion process is an ionic conductor.7. then the reduction reaction would stop. However. and the ionic conductor. the products of the above reaction often combine to form a precipitate: If the metal M represents iron (Fe).
1. making up 8090% of the cases in practice [2. . The most common forms of conosioii are the following 12*91: Uniform attack Galvanic attack Crevice corrosion Pitting corrosion Erosion corrosion Selective leaching e Stress corrosion 2. electrical neutrality is established. which is an aqueous solution simultaneously in contact with the anode and the cathode. 2. and can be prevented or slowed down most easily. therefore not one fixed point of deterioration. Corrosion cannot occur unless al1 of these four elements are present.1 Uniform Affack Uniform attack is the most common form of corrosion.91. This form of corrosion is easiest to predict. It is normally characterized by a reaction which proceeds uniformly over the entire surface of the metal.2 Phvsical forms of corrosion Corrosion can take various forms.2.the anode to the cathode via an ionic conductor. There is not one fixed point acting as the anode.1. Al1 points on the surface corrode at a sirnilar rate because every point acts altematively as an anode and a cathode.
If the two metals are not in contact with one another. the electromotive series.= Hg + e. the more anodic of the two metals suffers accelerated corrosion (anodic reaction) while the corrosion rate of the more cathodic metal decreases. they would each corrode at their own rate.= Mo + 2e.= AI Hf" + 4e.2 0.= Ag + Ze.+ e. Table 2. 0.= Nb Mn:' + 2e.= Sn + 3e.+ 3r' = In Cd:' + 2e.000 0.70 1.= U U" Be:' + 2e. However.= Na + 3e + 2e   Table 2.9.= n In3.71 Ca.'01.= Cr Zn2* + 2e.= Cr C i ' + 2e.1 Elrctromotive Strier "' 8 .= 2Hg + e. Standard Potenfial @(in volts) at ZS'C 1.136 C a .= Mn Zr" + 4e.= Cu + 2e. 1.53 0.= Zn Nb" + 3e.789 0.= Pb + 2e.1 is a reproduction of this senes.1.342 0.= Zr Ti:' + 2e.66 .50 1.= Ti Al3' + 3e.440 0.= Ni + 2e.521 0.= Ga Cr" + 3e.= Be Mg" + 2e.80 1.2 0.= Co n.2.= Fe Ga" + 3e. is consulted.1 1.250 0.= Hf + 3e.337 0.= Cu + te.277 0.= H: + 2e.= Mg Na' + e.53 1.2 Galvanic Attack Galvanic attack occurs wlien two different metals are placed in electrical contact in a corrosive environment [2.763 Ca.987 0. I n order to determine which of the two metals will corrode.336 0.= Cd Fe" + 2e. Elcctrode Reaction pi:Pd2' Hg:' AgHg:" Cu' Cu" 2H' Pb'Sn2' Mo'^ Ni:' Co" AU" = Au = pi + 2e'= Pd + 2e.37 2.800 0. which is an ordered list of each elements accompanied by their reduction potential.1.85 2.854 0.18 1. when they are placed in electrical contact.403 0.74 0.126 0.91 0.2.63 1.
or the effect of the formation of protective films which occur in the various environments. 3% Mo slainless steel. type 410 tactivel 5050 leadlin solder 188 stainlcss steel.2 Calvaniç Series for Seawater 12] . Bal.5% Sn1.Resist 1 3 5 Chromium stainlcss steel. Cu (Ambrac) 70% Cu3m Ni G88% Cu2% ZnIWt Sn ~comoosition bronze) 88% Cu3% Zn6. A more practical alternative to the electromotive senes is the galvanic series which is specific to a given environment. Table 2.3 N Cu (Monel) Titanium 18. Acliw (Read down) Magnesium Magnesium ailoys Zinc Aluminum 5052H Aluminum 3004 Aluminum 3003 Aluminum 1100 Aluminum 6053T Alclad Cadmium Aluminum 2017T Aluminum 2OXT Mild steel Wrought iron Cast iron Ni.2 indicates the galvanic series for seawater.A shorîcoming of the electromotive series is that is fails to take into account any alloying. typc 305 (passive) 188. typc 305 (active) 188. Nickel (passive) 76% Ni16% Cr7% Fe (Inconel 600) (passive) 7 1 % N i . type 316 (active) Lcad Tin Muntz metal Manganese bronze Naval b a r s Nickel (active) 76% Ni16% Cr7% Fe (Inconel 600) (active) Yellow brass Aluminum bronze Red brass Copper Silicon bronze 5% ZnZE Ni.8 stainless steel. type 316 (passive) Nable (Read cp) Table 2.5% Pb tcomp. 3% Mo stainless steel.
1. the reduction reaction cannot proceed because the dissolved oxygen is depleted. the rate at which the crevice metal detenorates is quite high when the crevice area is . the oxidation of the metal continues. The danger associated with this fonn of corrosion is that it is unpredictable. Furthemore. As the name implies.2. unifom attack occurs in the crevice. The electrons released in the crevice travel through the metal to a site outside the crevice where dissolved oxygen is present.2. and that the damage proceeds undetected because its location is well hidden. However.91.1 The Two Stages of Crevice Corrosion In stage 1.t .1b. The result is that the crevice continuously acts as the anode and suffers corrosion. However. I I . or at points of contact between the two surfaces [2. and reflects the site at which it occurs. corrosion occurs at crevices (openings of about 1 mm). The opening is suflicient to allow the corrodent to enter. Within the crevice. which are illustrated in Figures 2. while the remaining metal acts as the cathode and suffers no furîher damage. Corrosion o c c m in two stages. and stage 2 begins.la and 2.tapa. afier some t h e the stagnant water is depleted of the dissolved oxygen.3 Crevice Corrosion Crevice corrosion is highly localized. Water 1WZ//  Figure 2. but not large enough to allow the corrodent to flow.
2. and the tip of the Figure 2.1. Electrons move through the metal to the surface of the metal which is in contact with aerated water (cathodic site) and enables the reduction reaction to proceed.2. and grows downward.small with respect to the surface area in contact with the corrodent. which continue to grow undetected. It can cause equipment to fail because of perforation and it can be extremely dangerous when it occurs on vessels whose contents are under pressure.2.2 Pining Corrosion pit becomes the anodic site. This occurs because the crevice metal (anode) must produce electrons at a rate to satisfy the demand of the entire cathodic area. it can be difficult to detect because the corrosion products ofien cover the pits."1. Solids in the slurry erode (or scrape off) the protective oxide layers which form on metal surfaces.5 Erosion Corrosion Erosion corrosion is normally associated with moving çlunies [2. and stainless steel . Figure 2. 2. The stagnant water within the pit is depleted of oxygen. Furthermore.9. As in crevice corrosion. lead.91. These protective surface films provide metals such as aluminum. two local sites are involved [2.1. starts on It horizontal surfaces which can hold water under gravity.1 PifringCorrosion Pining corrosion is a highly localized generally form of corrosion. Pining is one of the most destructive forms of corrosion.2 illustrates schematically a metal undergoing pining corrosion. and at a surface discontinuity (scratch or dent).
The more anodic of the two metals will be the anode and will suffer accelerated corrosion.6 Selecrive Leoching Selective leaching is the removal of one element from a solid alloy. This dissolution occurs because graphite is cathodic to iron and a galvanic ce11 develops.4 Mirrortruîturc of Gray Cas1 lroo "' . Gray cast iron is composed of a network of graphite within a matnx of iron or steel. gooves following a distinct direction.12s131. Zinc. Corrosion occurs in the areas where the protective layer has been scraped off.12.3. is "leached out" and the resulting material is a porous copper matnx. therefore. It occurs when an alloy is composed of two elements far apart fiom one another in the electrochemical series.91. The graphite is in the form of flakes connected in such a way that the material is able to hold its shape as the iron dissolves 12. suffers corrosion as s h o w in Figure 2. i. the more anodic metal. leaving behind the more cathodic metal [2.4 shows the microstnicture of gray cast iron. Figure 2. Figure 2 3 Erorion Corrosion m Anodic Siics 1 Mctal Surface 1 2.9. An example of a metal subject to selective leaching is brass which is made up of copper and zinc. This fonn of corrosion is usually accompanied by surface striations.with their ability to resist corrosive environments. The exposed metal is anodic to the metal protected by the surface film and. lron dissolves Figure 2.e. Another example of selective leaching is the well known phenomenon of graphitization of gray cast iron.
the crack is said to be intercrystalline [2. When the grain boundary is anodic to the grain.91. in most cases. Furthemore.5a and 2. no corrosion would occur when a metal subjected to a weak corrodent is not subjected simultaneously to a tensile stress. One example of an anodic path is that of zinc in brasses. When the grain itself is anodic to the boundary. a weak nitrate solution will damage plain carbon steels. An anodic path can also be created when an element of an alloy precipitates at either the grain boundary or within the grain itself leaving one of the two areas anodic to the other. Each of these two components alone would not be problmatic. the reduced crosssectional areas are unable to withstand the design loads. then the crack is said to be transcryçtalline 12. which can be easily cut with a knife. stress are sufficient to cause severe damage [2.91. solid corrosion products which often accompany the corrosion process cause additional stresses by their expansive nature. not ail corrodent will affect al1 metals.7 Stress Corrosion Stress corrosion is the result of the combiied effect of a weak applied or residual tensile stress and a weak corrodent [2.91. the tensile stress in the uncracked section grows exponentially and can lead to sudden unexpected failures '2. voids and rut. but will not affect plain carbon steel at all.Ieaving behind a porous mass consisting of graphite. For example. but will not affect stainless steel at al1 [2.2. Stresses f?om 570% of the yield Another point of interest is tha: the corrodent is metal specific. Figures 2. n i e crack follows an anodic path. these matenals are not subject to graphitization. the graphite in ductile or malleable irons is in the shape of nodules or spheres. In addition. which is an alloy of zinc and copper.91. and moves downward. a weak chloride solution will cause severe damage to stainless steels. . As such. Like pitting corrosion.e. in contrast. but together they accelerate the rate of corrosion.1.91. When cracks begin to form. It has been observed that. the crack starts at a surface pit or scratch. 2. and a porous matrix cannot form. As the cracks grow under the combiied action of corrosion and stress.5b illustrate the difference between the two types of cracks. i.91.
This is the spontaneous direction for this particular system.1.Sb Tnnscrystallinc Crack 2. Some ofthis energy will be used up as the bal1 moves to position 2. stable ore +oxidation (2. a point of lowcr potential energy.1) This potential c m be compared to the potential energy of a sphere when held at an elevated position . Movement fiom position 2 to position 1 would not occur spontaneously in nature. and it can provide the potential 4 of a reaction. which is the ionic form. The metallic form of most elements is unstable.6. .'91 As seen in Figure 2.Figure 2Ja Intcrcrystnlline Crack Figure 2. Energy fiom an extemal source must be provided for such a movement to occur. at position 1 the sphere equilibrium is unstable and it possesses potential energy. and there is a potential for these metals to be oxidized: M unstable + + Mn++ ne' nahxal state.3 Whv do metals corrode? The electrochemical series indicates whether a metal is more anodic compared to another. But what does this potential represent and why does a metal corrode in the first place? Corrosion of a metal occurs because ofthe element's tendency to attain the natural state.
3a) By convention. and the other is an oxidation reaction. The standard most often used is the reduction of hydrogen ions: 2H'+2e+H2 fl I Position 2 Figure 2. For example: The potentials listed in Tables 2. for the following two reaction halves: It is useful to determine which of the two reactionhalves will be reversed such that the potential of the entire system will be nonnegative. A complete reaction is made up of two reaction halves. because they accompany only half of the overall reaction. . the value of the potential of this equation is chosen to be equal to zero volts. One reactionhalf is a reduction reaction.indicating the potential for the reaction to proceed spontaneously. It . &. i.Similarly. It must be noted absolute thatvalue. 4 . For exarnple. an Potentials of reactions are always measured with respect to a standard. the value of h e d is simply multiplied by 1.000V (2. electrochemical reactions are accompanied by a potential 4.6 Stable and Unstable Positions where 4=0. the potential but a relative 4 is notone.2 are termed halfce11 potentials.e. in tables such as for the electrochemical and galvanic series. To obtain the value of a particular oxidation reaction. . instead of oxidation potentials.d. proceed spontaneously. Another convention adopted is the used of reduction potentials.1 and 2. and the potential of other reactions are measured against this standard.
it is evident from the electrochemical senes that the reduction potential of both hydrogen ion reduction and oxygen reduction is higher than most metals of interest to engineers: The combination of one of the above corrodents with a metal whose reduction potential is lower than that of the corrodent will result in the oxidation. Corrosion rates are determined by studying the polarization behavior of the two reaction halves.is easily noted that if Equation 2.7a is reversed.000 V = 0. But of more interest to the corrosion engineer is the determination of the raie at which this corrosion will proceed. or corrosion.1.4 Determinina the Rate of Corrosion Examination of the electrochemical or galvanic senes enables one to determine whether or not a metal will corrode in a given environment. As seen previously. which is positive. the acidic solution and neutral aerated water. The system will spontaneously behave according to the following equation: When the two reaction halves are combined. the two reaction halves are the following: . + 4IrCd = (0. Retuming to the two most conunonly encountered corrodents. the one with the srnaller reduction potential will be reversed and the element will undergo axidaiion.440 V) + 0. the total potential of the system will be equal to 4. 2.440 V. of that element.
+ Cu Pnor to electncal contact of the metal rods. a CdZn banery is ions (a solution of CuSOd). the two separate systems are at equilibnum. AS seen in Figure 2. it is observed that the reduction potential of Zn is lower than that of Cu. The driving force of (+c. enswing electncai neutraliiy. and copper to be reduced according to the above I Oxidation +& = 0. Once the two metals at different potentials are placed in electncal contact. The two solutions are co~ected by a diaphragm which allows the passage of ions. ) volts will cause Zn ta be oxidized.9.7. and no corrosion is occurring.+ neANODIC REACTION: M + Mn+ CATHODIC REACTION: Acid solution: OR Neutral Aerated Water: 2H++2e'+H2 112 0 2 + HzO+ 2 e' + 2 O K Oxidation of metal M ' Reduction of H Reduction of Oz In order to fully understand the above corrosion system. From the electromotive series. an analogy will Grst be made with the copperlzinc banery [2.9b) R 4 Control of resistance T"'_rl Figure 2.76 V Reduction = 0.'48'51.9a) (2. the system will attempt to reach a point of equilibrium at a potential somewhere between +a and +c.34 V (2. The two resulting equations are: Zn + Zn2' + 2 ecu2++ 2e.7..7 Schematic o l a CulZn Banery . and a made up of a copper rod immersed in a solution of CU'' Zn rod immersed in a solution of 2n2' ions (a solution of ZnSO4). and therefore Zn will be anodic to Cu and suffer oxidation. . .OZ.
10) . the open circuit at I=O. and 3.8 $ vs. The electrons travel through the wire to the surface of the copper rod.91. the short circuit at I=Imax. i. the system is manipulated by varying the current permined to flow through the wire. where they combine with the cu2+ions from solution. obtained by Figure 2.e. Open Circuit The point on the diagram representing an open circuit is at I=O. When Zn is oxidized. It is observed that the potential of each of the metals is the standard Nernst potential which is defined as [2. 1.8 is ploning the potential of Cu and Zn venus the registered current [2. As the electrons travel through the wire. Three distinct points on the diagram are of interest: 1. and the two metals behave independently. a log l point of restricted Figure 2. a current is registered by an ammeter. log 1 for CuRn Battery current flow. to form Cu.303 RT/nF * log [a&a. 2. via various resistors. In order to study the variation of the potential with current.equations.91: = I$N $NO + 2.d] (2. This represents the behavior of the system when electrical contact is not provided. electrons and 2n2' ions are released. when no current flows.
314 Jtdeg mole) T = absolute temperature (K) n = number of electrons transferred F = Faraday's constant (96500 Cleq) &% = activity. of reduced species a.12) + 0.10 becomes: (2.059212 log CU^'] 2.where $N = Nernst potential = $NO Standard Nernst potential (equilibnum potential of metal in contact with its own ions.1 1) + 0. termed the overvoltage q. Point of Restricted Flow Between 1=0 and I=Imax. the change in potential for e x h metal. or concentration. Equation 2. For the reduction of Zn at 25 OC: Zn =$ N ~ O t zn2* + 2 e. the Nernst potential is calculated for both the Zn and Cu electrode.14) . The denvation of the following equations c m be found in Appendix A. at unit activity) R = Gas constant (8. the current is manipulated to flow at a predetermined rate.1 O becomes: (2. of oxidized species or concentration. = activity. can be calculated as 12s91: f)~u = $8 W n = $b .$NU $~zn (2.059212 log [zn2'] Cu t For the reduction of Cu at 25'C: 4h. the current is allowed to vary and the potential of each metal is measured and ploned versus the current. From the diagram. Equation 2. Using resistors.c" = ~ N C " ' cu2++ 2 e..13) (2.d For the CdZn banery..
When a metal M is placed in an acidic solution.. . The current is govemed only and the current by the potential difference of the system. the following reactions occur: Since the reduction potential of H 'is larger than the reduction potential of most metals of interest. The following diagram will result: Figure 2. This situation is the fiee corrosion situation. and the reduction of 0 2 in a neutral aerated solution.e..9 Poiarization Diagram for Corrosion in Acidic Solution .3. I. the resistance R=O and the current FI. . The equilibrium potential is called the free corrosion potential. The above analogy can serve to better undersland the two corrodents îhat are most commonly encountered by corrosion engineers: the reduction of H 'ions in an acidic solution. i.. associated with 4 is the corrosion current.. Short Circuit The point of short circuit is the point when the current is allowed to fiow unresinctedly. the metal will undergo oxidation (anodic reaction). & .
10 Polarizalion Diagram Tor Corrosion in Neutra1 Aerated Water When the system is allowed to corrode freely.g. in the case of corrosion in acidic environments.will apply. n i e derivation of the above equation can be found in Appendix A. When a metal M is placed in neutrol oerored water.$ current I. the potential. rainwater or seawater. e. the Nernst potential of H 'reduction becomes [291: It is very interesting to note that. the potential. Furthemore. .will and the corrosion apply. the following reactions occur: Since the reduction potential of O2 is larger than the reduction potential of most metals of interest. the metal will undergo oxidation (anodic reaction). The following diagram will result : Figure 2. the Nernst potential depends only on the temperature and on the pH.$ and the corrosion current Ic.When the system is allowed to corrode freely. Fwthemore.. .. the Nernst potential of O2 reduction becomes [2.91: .
dependent on the value of i. Electrons travel through the metal from the anodic to the cathodic sites.and exchange current density. the exchange i .91. 1 . I . 2.303 RTl4F log {PO~/[OHJ~} where PO2 = partial pressure of oxygen in the solution. Consequently. i. Ison increases as increases. Figure 2.1 1. In reduction and very reactions such as H' 02 reduction.. Although no changes are visible to the naked eye. the corrosion current. $N. which A term that appeared ofien in the previous polarization diagrams was ions. An example of this is a Cu rod placed in a solution of CU" ions (a solution of CuS04). pH (or pOH). log 1 schematically in 2. is current density... which are continuously changing locations.. This rate is termed the exchange current density.5 The Exchanee Current Densitv. represents the exchange current density. As it is s h o w Figure i. the Nernst potential depends on the temperature. apply 12. the Nerst potential. The equilibrium reached is a dynamic one. is highly Furthemore. of the metal sensitive to the condition surface. the rate at which a metal 22 . In the case of corrosion in neutral aented water. IO. .11 Dependence oll.4 ~ 0= 2 4~02' + 2. When a metal is in equilibrium with its o u n i.1. on the value 01 i. reduction and oxidation of the metal are taking place at equal rates. and the partial pressure of oxygen in the water.
The shape of the polarization lines are determined by either concentration or activation polarization. so that variations in 1 .. The Tafel equation relates the overvoltage q to the current density r by the following equation: . the diagrams are similar in that each of the two lines is represented by a straight line.will corrode varies as the surface preparation of the metal varies 12*91. As mentioned previously. This behavior is termed concentration polarization. t2. i n fact.91. it is very important to ensure that the surfaces of the samples are prepared consistently. where A is the surface area of the Activation Polarizotion Activation polarization.1 represents the corrosion current demity.1. the term I . * A. For the sake of compatibility in calculations.1. anode. makes up 90% of the cases. or Tafel behavior.6 Determination of & I . the corrosion current. is used instead of Lon. This will be correct in approximately 90% of cases in which activation polarization behavior governs 12. the electrochemistry of the system govems the rate which a slow species can move through the solution.The term r. and it is diiectly proportional to Lon. This behavior occurs in well stirred solutions. are obtained fiom the intersection point between the anodic and the cathodic lines of polarization diagrams. determination of Ln. and it occurs when the rate of a reaction is controlled by the slowest of the steps in the reaction sequence. When testing metal samples to obtain Ln. both behave linearly.e. an altemative to this situation warrants some attention.and 4 .6.91. Le. the values of L . both the reduction and the anodic reactions display Tafel behavior. i. Up to this point. Ln =r . will not introduce errors in the 2. 2. However. where the reaction rate is not limited by the speed at In activation polarization.
IN HC1 2N Hzso4 1N HC1 1N 0.? = P 1% (i/b) (2. .$ i .3 shows some typical values. . and the and i . .17) where p = Tafel constant. or Tafel dope [2s91.12 shows a typical diagram in which activation polarization govems. are obtained: . In order to solve for values of . The values of P have been tabulated for the vanous metals in different media. Metal 1 Temperatore (OC) Solution 1N HC1 0. IN HC1 0. Table 2.1N HC1 1N HCI 0.01SN HCI Table 2. the following two equations are solved simultaneously.3 Typieal p Values l4 Figure 2.
13.2 lcon log 1 O ' Figure 2. A typical diagram is s h o w in Figure 2.1.6. O Icorr=l~ log 1 Figure 2. only the reduction reaction is affected. The oxidation reaction exhibits Tafel behavior as it did in the case of activation polarization.I 2.13 ConecntrationPolarization Diagram 12'91 .12 Activation Polarizntion Diagram Concentration PolarCation In concentration polarization.
I.14 Distribution of H The rate at which certain species (in this case the H ' ion) are able to diffuse in through the boundary layer will govern the rate of the corrosion reaction.Concentration polarization usually governs in cases where the solution is stagnant. if the governs. The maximum expected current in concentration polarization cases is called the limiring current. Figure 2. in corrosion due to H ' reduction where the solution is stagnant. For example. the initial condition is represented by Figure 2. As a consequence. i.14a. it is said that mass transfer controls the rate of the reaction..e. * Distance from metal surface 'ions in Time Figure 2. as H 'reduction occurs at the surface of the metal.13. a thin boundary layer is formed in which the concentration of H 'ions varies iÏom the concentration H 'in the buk solution. Distance from metal surface 1O IH'I.. This concentration gradient causes ions to diffuse towards the surface where they are then consumed by the corrosion process. . i. As it can be seen in Figure 2. H ' ions are used up. towards the metal surface where corrosion occurs [291. The rate of the reaction depends on how quickly certain species are capable of diffusing îhrough the stagnant solution. solution had been well stirred. However.14b illustrates the boundary layer in question. concentration polarization. 0 1 . [H+]b. 10 zero. when concentration polarization is srnaller than it would be if activation polarization governed.
the value of PO2. They help one visualize electrochemical phenomena which would otherwise be quite abstract. 4 ~ 0 12. passivity.4 atm in air). of the reduced species 2. r galvanic anack.91: 11. = activiîy.7.91: 2 . r 0 2 solubility. and r chloride content. Polarization diagrams also help visual understanding and prediction of the effect of varying certain parameters influencing the corrosion rate in the two corrodents of interest.1. affects only the value of the Nernst potentiai.1. 2. or concentration. the partial pressure of oxygen (1 atm for pure oxygen.The limiting current densities for the reduction reaction can be calculated from the following equation [2. The parameters discussed in the following sections are: r POz and Hiconcentration.7 Effect of Varvine Parameters Using Polarization Diaerams Polarization diagrams have many uses. = knF [arc& (2.1 9) where k = mass tmnsfer coefficient (cmlsec) n = number of electrons transferred in the reduction F = Faraday's constant (96500 Cleq) [ a & . r r multiple corrodents.1 PO2 and Concentration In cases of corrosion in neufral aerafed water. 0. acidic solutions and neutral aerated water.
. IL. so does the value of bol.. I increase in. and the vertical portion of the reduction cuve is shifted to the nght. the value of IL increases as well. . for activation and concentration polarization. In the case of activation polarization. the Nernst potential $NH+ increases ($NH+ = 2.15a and 2. because as the value of [H+Ib increases.h 0 2 =h O 2 O + 2... This is illustrated in Figures 2. and this causes the cathode line to shift upwards. n i e verticai In cases of corrosion in acidic solutions. The above results also apply in the case of concentration polarization because. the results of increasing PO2 are as follows: increase in I. no change in 10. This results in the reduction lines shifting upwards. 0 .15b. so does the value of [02]b. $ . I no change in no change in the anode line. as the concentration of H' ions increases and the pH decreases. the results of increasing the concentration of H' are as follows: increase in. respectively. In the case of activation polarization. and this leads to an increase in line is therefore shifted to the nght.303 RTl4F * log { P O ~ / [ O H ~ ~ } As the value of PO2 increases. 0 . The above results also apply in the case of concentration polarization. as P02 increases..303 RTE * pH). no change in the anode line. increase in. . $ .
= 0. = l atm (bubbling O.21 atm (air wtunted water) log 1 increases mm 1 l corr InCrePSeS I I log t Figure 2.increases increases PO.) 1con lncreases I I I 1 I PO.15 Elleel of Vsrying PO1 .
3 Multiple Corrodents Situationswhere a metal is subjected to the effects of more than one corrodent are not uncommon. \ Fresh : . where the 0 2 cases of corrosion in neutral aerated concentration The varies with polarization govems.91. acid rain is a corrodent rich in both oxygen and H+ ions. Consequently.1. the PO2 is kept constant. two cathodic reactions occur simultaneously 12. this will result in an increase in 2. solubility of 0 2 O. For example. in this case.91.16 I Variation olOl Solubility with NaCl Concentration 0 2 Assuming a constant PO2.91: . in such a case. The 0 2 solubility is highest at approximately 3% NaCl content.3% % NaCl 1 O I Figure 2. an increase in the concentration of dissolved causes an increase in IL ( 1 ~ = k n F [ 0 2 ] b in the water ).7. which corresponds to typical seawater [2.16. Solubility chloride content as illustrated in Figure 2. 1 6 . The solubility of affects only water. [OH] and temperature. but the solubility of Oz varies dependiig on the presence of impurities such as chloride ions in the aqueous medium [2.This parameter must not be confused with PO2 studied previously.
This line is used to determine the actual current density existing at the metal surface..respectively. the total current density of the oxidation of the metal..17a illustrates the situation of multiple corrodents in cases where activation polarization governs. This conclusion is more easily The new line i. is equal current densifies of the reduction of 0 2 and H ' .. increase.. and ib at any given value of 9. representing the situation of multiple corrodents has. reached when studying the polanzation diagram in Figure 2. only one anodic reaction is involved: M +M''++neo Figure 2. shows clearly that when a second corrodent is introduced in a system. the result of addiig a second corrodent to a system is to increase both t. Figure 2.17b. the value of and 4 . a new reduction l i e must be drawn.17a i. . In cases where concentration polarization govems. This line is constructed by addiig i. In situations of multiple corrodents acting simultaneously. The value of to IO>+ t ~ +the . and 9. Another interesting point to note is that the reduction of that does the reduction of H 'ions. t. 02 ha a higher contribution to t. The terms ta and ib on the polarization diagram represent the current density that would apply if one corrodent was acting at a time... which is equal to 102 +i ~ + . . a constant value of rotai.However. as before..
Figure 2.17 Elleet of Multiple Corrodentr 19] .0 0 1con H4 1con O* log t l con t a u 1 O I I I I ! ! ! Iranuitai log t ~ r o n KIcon0.
1. H 'or and two anodic reactions: The resulting corrosion system is illustrated in Figure 2. In this case. If only metal Mi is present.4 Galvanic Atrack Galvanic ûttack occurs when two metals are placed in electrical contact in the presence of a corrodent.2. there is one cathodic reaction (reduction of 02).18.7.18 Galvanic Attark 19' . Figure 2. while if only metal M 2 is present. lines 2 and 4 would apply and i ~ would i result.
such as Fe. Lines 3 and 6 are obtained by adding the value of the curent densities of lines 1 and 2. will increase and the rate of corrosion of the more cathodic of the two. Passivity is the formation of a protective oxide layer on the surface of the rnetal which causes it to corrode at a much slower rate than that predicted by Tafel behavior [91. Many metals. then lines 3 and 6 would apply. considered so far. M*. Cr.91 The currents in this region vary between the exchange The active region. Three distinct regions can be discemed: the active region. will decrease. Figure 2. Ni. It can be seen that when two metals are involved. Metal Ml is said to suffer accelerated corrosion. exhibit passivity in various conodents.19 Polarization Diagram of a Metal Exhibiting Passiviiy 12. Ti. Ml. the rate of corrosion of the more anodic of the two metals. 4NM. When both metals are involved. and the passive potential. . the passive region.. is the region limited by the Nernst potentkil. and Al. or galvanic atta~k[*~]. and the transpassive region. respectively. and lines 4 and 5.lines 1 and 5 would apply and I ~ Q would result [91.19 illustrates a typical polarization line of a metal which exhibits passivity. 4. Figure 2..
6 Chloride Content The effect of the presence on chloride ions in a solution. Co. The value of the potential of the system will determine whether Oz or C1' ions will be adsorbed. The passive q i o n is the region limited by the passive potential. $ . of the metal in the given solution.. chloride ions favour hydration of the metal ions and therefore increase the rate of dissolution I2l.7. The passive layer forms due to the absorption of oxygen onto the metal surface.19. The value of the current is not constant in this region. andlor prevent the formation of a passive layer in metals such as Fe. Passivity is due to the adsorption of Oz onto the metal surface.. 1 . and the cntical current density. occurs at potentials between Op. 6. Chloride ions break down. i. .and does not vary with potential. but increases with increasing potential. This adsorption . obtained when the intersection of the two polarization lines occurs within the passive . 1 . they compete with 0 2 for absorption Iz1. I. . Le. Unlike the adsorbed Oz which causes the rate of the metal dissolution to decrease.. the lower is the value of i. . at which point passivity begins to breakdoun. and $ As it can be seen in Figure 2. chloride ions cannot displace the adsorbed OZand the passive layer will remain stable and . Below a certain potential.. In this iekion. In this region. and the transpassive potential. The transpassive region is the region where the potential is higher than O The breakdown of passivity begins at $ . is to increase the value of the exchange current density. 2. Ni. when the adsorbed layer of Oz is no longer stable and begins to disintegrate Iz9]. L . whether passivity will form or breakdown. Cr.the lower is the value of region..current density. When chlorides are introduced into the solution. and to breakdown its passive layer Iz1. the current is equal to the passive current density. and stainless steels. the metal exhibits siandard Tafel behavior.1. and to a lesser extent halogen ions.
Species such as N O j and SOJ'. i .ions are capable of Breakdown of passivity occurs locally and is not spread out uniformly over the metal surface. the higher the current flow at any pit. At potentials higher (or more noble) than the critical potential.e. there are two methods used to obtain the corrosion rate electrochemically: Tafel Extrapolation. CI.e.ion anack is the addition of extraneous anions to the solution. results in a situation of accelerated corrosion. thus destroying the passive layer. inhibit the formation of pits. the remaining metal surface. . have been obsewed to corrode at rates similar to those of metals that do not exhibit passivity at al1. and Liiear Polarizztion [9s'61. the current resulting fiom the metal oxidation is equal in magnitude to the current feediig the reduction of the corrodent. . and large cathodic area. the theory behind the corrosion rate measurements is outlined.ions for sites on the passive film and. An effective inhibitor for unit area is smaller for deeper pits than for shallower ones 1 Cl.20a that at this potential. . Furthermore.4 This can be seen on the polarization diagram of Figure 2. at this point of equilibrium. This potential is termed the cntical potential . This current is termed the corrosion current density.corrosion will be negligible. compete with Cl. which will not break down the passive layer. the pit. i. the less likely that other pits will form nearby. Essentially. A metal which is exposed to a corrodent such as an acidic solution or neutral . l ' [ The effect of Cf ions can be so pronounced that in some cases stainless steels. Destruction of the passive layer tpically starts at a point of discontinuity i l m . which are known for their resistance to most corrosive environments. It is on these basic principles that corrosionmeasuring equipment are developed. The result is localized attack and the formation of pits in the passive f [21. consequently. This combination of snall anodic area. aerated water will acquire a certain potential. . the electrons are being produced and consumed at the same rate. the number of pits per 2 ] . l ' [ 2. l ' [ displacing adsorbed 02. i.2 Measuring Corrosion Rates In this section.
This phenomenon is called anodic polarization potential is decreased below . When the potential increases then the cment leaving the anode will increase. ïhis phenomenon is called cathodic polarization[9. . then the anodic and cathodic currents. Figures 2. Conversely.21 would be obtained. . will no longer be equal and a net current. and i.20b and 2 . When the potential is equal to g no net current is expected to flow.$ represents the region of cathodic polarization. causing the metal to dissolve [9. . is applied. above it represents the region of anodic polarization.O . The section of the curve below . 2 0 ~ illustrate this point. i. and the section . will flow.161.If the system is manipulated such that a potential 4. a curve resembling Figure 2. other than + .. if the then the cment leaving the anode will decrease and the metal will dissolve at a slower rate. The above theory forms the basis of the two methods used to determine corrosion rates electrochemically: Tafel Extrapolation and Liear Polanzation. above + more quickly. i.'61. if the imposed potential is varied and each value is plotted against the logarithm of the resulting current.
COLT 1% ' 1 I I log 1 la lc lcorr .20 variation of 1 . log t la lcon lc (cl Figure 2. wilh Potential E$ 38 . and 1 .
schematic diagram in Figure 2. such as graphite or platinum. for the resulting current measures the potential i. The very simplified The reference electrode 4 of the metal. Finally. The purpose of this electrode is to act as either a source.22 illustrates the typical setup. Simultaneously. an ammeter records the current flow to or fiom the working electrode.I K Cathodic Polarization Figure 2. and a potentiometer records these values. or a sink. It is placed in the corrodent along with the awiliary and the reference electrodes. in the case of anodic polarization. The metal under study is called the working electrode.1 Tafel Extrapolation In Tafel Extrapolation.2 1 Tafel Curve Anodic Polarization ofmetai M / log t 2. The auxiliary electrode is usually made up of an inert metal.2. a potentiostat is used to impose the desired potential on the system. corrosion rates are measured using data obtained by polarizing a metal sample cathodically and then anodically. . in the case of cathodic polarization.
and it is measured by the reference electrode. The result of ploning the imposed potential versus the logarithm of the resulting current is the complete curve illustrated in Figure 2.Figure 2.. .. i. is to determine the value of &. potential reaches 4 + A$. prior to polarizing the metal sample. This continues until the and $. = ic= i .$ There is no net flow of electrons. The potential is then increased by a predetermined increment. . The metal sample is placed in the corrodent.A4 for a specified amount of t h e .+A$ . and the anodic and cathodic reactions are allowed to proceed undisturbed.23. This situation is represented by point a in Figure 2.. is and the . a. and the value of the resulting current. recorded. The potential remains at $. the potentiostat then imposes a potential of $conA4.. Once the value of... and the potential is allowed to attain its equilibriurn.22 Schematic of Setup for Tnfel Test ['61 The first step.$ resulting current is again ploned at this new value 4 value.$ .e.23.. . . is recorded. ia This potential is called the opepl circuit corrosionporenrial. and thus al1 potential values between $A$ have been scanned. and $ = .
The 0 x 1 1 50 to 250 mV. Ig1 . This region of linearity is called the Tafel region. ... Typically.23 Tale1 Curve Obtained by Varying @ . The slopes of the cathodic and anodic polarization lines in the Tafel regions are termed P. and ends when the various phenornena cause the linearity of the curve to be lost. Figure 2.. or more. Once the value of i. g. where the two l i e s intersect.g. can be computed. . . However. e.. this curve is nonlinear.24. the Tafel region begins at value of Ag can range 6 +. respectively.. The value of i.$ and 1 = I.. f .Figure 2. and Pa.50 mV. . At low currents. is obtained by extrapolating the Tafel regions back to the corrosion potential.. the corrosion rate in mm/yr. the two branches of the curve become linear at higher current values. the potential attained encourages the formation of a passive layer and the cuve suddenly continues vertically upward (current does not increase with increasing potential) f9.'61.. Another mical curve is illustrated in Figure 2. is known.25 shows the intersection of the two dashed lines at a point where $ = .
25 Obînining i .24 Tafel Regionr 19J61 Figure 2. log i O Figure 2. .Tafel ' . from the Tafel Curve 19"q .
26 Linear Polarization Curve . ($con .2 Linear Polarization An alternative to Tafel Extrapolation is the method of Linear Polarization which has been studied extensively to date. The procedure is the same as that for Tafel Extrapolation with the following exceptions 19. and not on a linearlog plot. $ is recorded. The $ values and corresponding are ploned on a linear scale and the resulting graph resembles Figure 2. the potential is dropped to ( $ .'? O O n i e value of A$ is approximately 1010 mV. once the value of . It is then raised incrementally up to a potential of + 20 mV). and the current is recorded at each step. The values of p. but must be k n o m or estimated before hand. are not obtained automatically. ivalues 4 corr + AI$ 4 corr 4 corr .26.20 mV). In the method of Linear Polarization.2.2. and p.A$ Figure 2. O The data points obtained during polarization are ploned on a linearlinear paph.
The most important ones are the following: the formation of differential aeration cells. Le. selective leaching. The deterioration of metal pipelines in soils can be due to many phenomena. and r stresscorrosion cracking.1 Differential Aeration Cells When a pipeline is exposed to conditions which vary along its length. The values of p. can be either determined by the method of Tafel Extrapolation. with A+ i :20 mV. This results in potential differences and.3 Soi1 Corrosion and Its Effects on Underground Infrastructure This section deals with the principles of soi1 corrosion and its effects on the underground infrastructure. [ ~ ~ ' ~ .3. %. the corrosion in the pipe section located in the area of low 02content.' ~ ' : where the term (A+ 1 Ai) is also called the polarization resistance. Stem and Geary (1957) derived the following relationship to obtain the value of I . .Under these conditions of slight polarization. the potential varies linearly with the resulting current. can then be computed. 2... and the corrosion rate in mmlyr. 2. The value of i. The various mechanisms of soi1 corrosion are outlined and explained from an electrochemical perspective. or it can be estimated.91. it can be subjected to variations in the 0 2 exposure 112. consequently. . r galvanic attack. is determined by the StemGeary equation. given in ohms. and p. Underground pipelines make up the greatest proportion of the metals threatened by soi1 corrosion.
ï h e section of pipe located in the clay will have a lower potential (since the O2 concentration is loaer) than the section in the sand. A cell is. from the bonom to the more aerated crown. Another cause of differential aeration cells is the improper installation of new pipes[71. the section in the clay will be anodic to the section in the sand. When a pipe rüns through both of these soils. Once again. consequently. and the groundwater will serve as the ioNc conductor. and the groundwater as the ioNc conductor. . Electrons move through the pipe itself. and localized corrosion will proceed at an accelerated Pace II1. Pipes are usually rested directly on undisturbed soi1 and then covered with relatively loose backfill. such as a parking lot or a street ['l. and will contain higher concentrations of oxygen. A corrosion cell is therefore set up with the pipe beneath the pavement being anodic to the surrounding pipe. n i e pipe itself will serve as the electrical conductor allowing electrons to move from the anode to the cathode. formed with the pipe bottom being anodic to the pipe crown. The circuit is completed. Different soils have different porosities and therefore different 0 2 contents. On the other hand. For example. a corrosion cell is created. undisturbed soil. which is more readily exposed to air and oxygennch rainwater. the pipe itself acts as the electncal conductor. and corrosion will occur in the pipe located in the clay. clays typically have very low porosities and. therefore. The soi1 beneath the paved surface generally has a lower oxygeri content than does the soi1 beneath the unpaved surface. with the groundwater acting as the ionic conductor. As a result. low O2 concentrations. and generally contain higher levels of 02. A similar situation may be created when a pipe passes under a paved surface. The backfill is generally more permeable than the compacted.A situation which is often faced is a pipe which encounters different soi1 types dong its path. This explains why most corrosive attacks on pipelines occur on the bonorn 114 of the pipe. sands are highly porous and well aerated.
2.8 to 1. Before long. The old pipe is the cathode. and the groundwater is the ionic conductor. being cathodic to iron. over the years a protective surface film has formed on the surface of the old pipe. the metallic crossover is the electrical conduc:or.1 V. . Another example of galvanic attack is the accelerated corrosion of iron pipes placed in contact with a soi1 containing cinders [Il. This situation is often encountered when the capacity of a water pipe is insufficient and an additional water pipe is laid parallel to the old one and the two are connected by crossovers. while the rate of corrosion of the more cathodic metal decreases A common example of galvanic attack is the corrosion of steel (iron) water and gas mains at the point of contact with the copper pipe services [Il. galvanic anack may not be suspected because the matenals are not different.1.3. even if the pipes are niade of the same material [Il. providing passivity and resistance to corrosion. At first glance. The old steel is therefore cathodic to the new steel. Luckily. galvanic attack occurs when dissimilar metal are placed in electrical contact. and the corrosion is spread out over a large area. which can cause very senous damage to the pipe. which will suffer accelerated corrosion when the pipes are in contact with one another. As it was descnbed previously in Section 2. The potential difference between the two metals is in the range of 0. this situation does not cause too much damage because the area of the anode (the iron pipe) is much larger that the area of the cathode (the snialler copper line). will result in the iron pipe to suffer accelerated corrosion. and are therefore cathodic to the iron pipe. and exposed to a corrosive environment.2. Galvanic attack can also occur when a new pipe is placed in electncal contact with an old pipe. The more anodic of the meials suffers accelerated corrosion.2 Galvanic Attack Another very common rnechanism of soi1 corrosion is the phenomenon of galvanic attack. Cinders are essentially made up of carbon. the new pipe is the anode.2. leading to the erroneous conclusion that the pipe material itself is to blame. Copper. However. the new pipe may be in worse condition than the old one.
1.91. The weak corrodent is usually neutral aerated groundwater.3 Selective Leaching Selective leachiig. 2.6.2.3. Cast iron is composed of graphite flakes within a matrix of iron. it leaves behind a weak porous material which is characterized by a dark gray color. f i s c m result in significant residual stresses forming at the bends of the pipes.4 StressCorrosion Cracking Stresscorrosion crackiig (SCC) results when a metal is subjected to a combination of weak corrodent and a weak tensile stress apparent. as described in Section 2.2. failwe c m appear quite suddenly because no general surface corrosion is When underground pipes are manufactured.7. As iron dissolves. leaving behiid a porous mass consisting of the more cathodic element. Also. [1s2.As described in Section 2.2. Graphite is cathodic to iron. An example of localized stresses in buried pipes is "cold bendiif of pipes [ ' l . This occurs because the alloy is composed of elements whose potentials are very different.3.1. resulting in the more anodic of the two beiig "corroded". An example of this is the graphitization of cast iron pipes [ I l . The result is the accelerated corrosion of the pipe in the areas where the pipe is subjected to tensile stresses. . These forces are suficiently large to cause serious SCC problems. is the removal of one element îÏom a solid alloy. therefore a galvanic ce11 exists. the pipe c m be subjected to localied stresses when they are forced into alignment once placed in the ground. a weakly acidic groundwater. they are often subjected to "cold bending" to produce bends.
an index of 10 or more indicates that the soi1 tested is corrosive. and as such. Typically. a a a oxidationreduction potential. Nonethelass. and Germany. This section deals with the factors tested and the points allocated to each.4. ïhis project focuses on these two standards. the AWWA standard is used extensively in North America. and a fmal corrosivity index is reported. although the testing proceedure may vary. the variables tested are the same. many different standards have been developed in North America.4 Standards for Determining Corrosivity of Soils The majority of the standards for determining soil corrosivity were designed to respond to a particular need. Two standards which are used extensively in Quebec are AWWA Cl05 and PACE 823. and as such. It mus1 be kept in mind that the AWWA is a pnvate organization and not an independent national entity. PH. A detailed description of the testing procedure is presented in Chaprer 3 : Procedures and Apparatus.2. The following soi1 characteristics are considered: .1 AWWA Cl05 The Amencan Water Works Association (AWWA) Standard was designed to assist the engineer to decide whether or not to use polyethylene pipes instead of traditional materials. The points are then sununed. a These soil characteristicsare evaluated separately and the appropriate point is allocated to each result dependig on the extent to which the factor contributes to the corrosivity of the soil. France. and sulfide content. The soi1 characteristicsexamined in the AWWA Standard are the following: a soi1 type. 2. drainage ability. whereas an index below 10 suggeststhat the soil is not corrosive 1251. soil resistivity. the grid developed may be biased to some extent. According to the AWWA standard.
O
Soi1 type is a characteristic which is recorded in the AWWA grid, but which is not
allocated any points. The type of soil (sand, clay, silt) is reported along with the following characteristics: color, odor, presence of rocks or pebbles, and the presence of organic materials. The drainoge ability of a soil estimates the ease in which the soil is penetrated by water. The better the drainage ability of a soit, the less Iiely that a soil will become anaerobic and permit bactenal corrosion. The drainage ability is classified as either excellent, good or poor, and the following points are allocated:
O
Excellent
1
O
I
O
Soil resistivity is a measure of the ability of a soil to conduct a current. The lower the
resistivity of a soil, the beîîer are the soil's electrolytic properties, and the higher is the rate at which the corrosion can proceed. Soil resistivity is measwed in ohmcm, and the following points are allocated:
r
The pH of a soil is a rneasure of the H+ion content of the soil. H+ion reduction is an important reaction in the corrosion process. The following points are allocated to this factor:
r Oxidationreductionpotential,
or redox potential, is a rneasure of the potential
+ of
the soil. The potential of a soil indicates whether or not a soil is capable of sustainiig sulfatereducing bacteria, which contribute greatly to the corrosion problern. A low potential indicates that the oxygen content of the soil is low and, consequently, the conditions are ideal for the proliferation of sulfatereducingbactena. The following points are allocated:
The sulfide content of a soi1 serves as an indicator to the presence of sulfatereducing bacteria. The greater the sulfide content, the greater the possibility of the presence of sulfatereducing bacteria. The following points are allocated:
When sulfides are present and the pH of the soi1 lies between 6.5 and 7.5, an additional 3 points shall be added to the calculated index. These points are added to account for the fact that the conditions are optimal for the proliferation of sulfatereducing bacteria.
2.4.2
PACE 823
The PACE 823 standard was designed to assist the engineer in the decision to provide protection to buried steel reservoirs, such as a petroleum tanks. In the original standard, three soil samples are taken £rom the site and tested in the laboratory. Each soil sample is tested individually, and the results are compared with those of the other two samples. The three samples are originally located at a distance of 30 meters £rom one another, and their locations form an equilateral triangle when viewed from above.
An adaptation of this test was used in this project. The soi1 samples were received
and tested individually, with no comparison made between samples. The soil characteristics examined in the PACE standard are the following: moisture content, soi1 resistivity,
0
pH,and sulfide content.
These soi1 characteristics are evaluated separately and the appropriatepoint is allocated to each result depending on the extent to which the factor contributes to the corrosivity of the soil. The points are then summed, and a final coaosivity index is reported.
A deîailed description of the testing procedure is presented in Chapter 3 :
Procedures and Apparatus. This section presents the factors tested and the points
allocated to each. The following soi1 characteristicsare considered: The moisture content of a soil describes the state in which the soi1 is received in the laboratory. This parameter indicates the extent to which a soil is saturated during the year. The soil is classified as either dry, moist or saturated, and the following points are allocated:
I
r
Moist
2
1
Soi1 resistiviîy is measured in ohmcm, and the following points are allocated:
r
The pH of a soi1 is a measure of the H 'ion content of a soil. The following points are allocated to this factor:
The sulfide content is classified as positive or negative. The following points are allocated:
1Sulfide Content 1 Points 1
CHAPTER 3: PROCEDURES
AND APPARATUS
The various laboratory experiments performed, the apparatus and the matenals used, the purpose of the experiment, and the results obtained are described in this chapter. For each soi1 sarnple collected, the following variables were evaluated: soi1 type, drainage ability and moisture content, pH: direct and saturated, oxidationreduction (redox) potential: direct and saturated, resistivity: direct and saturated, sulfide content: using HCl + lead acetate paper, and a solution of iodine + Na3N, concentration of C1' ions, rate at which a standard metal sample will corrode in the given soil using the method of linear polarization, and calculated corrosion indices according to the AWWA and PACE methods.
3.1
Soil Samples The soil samples tested were obtained fiom the various regions of Quebec. In
most cases, the samples were taken for the purpose of beiig tested according to the AWWA or the PACE methods by COREXCO, Montreal, to determine the need for cathodic protection of various metallic structures embedded in the given soil.
i n total, 153 soil samples were tested. Of these, only 75 were available in
quantities sufficient enough to permit testing for the corrosion rate using the method of linear polarization.
3.2
Soil Type During the course of al1 of the tests to follow, the technician should observe
certain characteristics that will enable the determination of the soil type, i.e. a sand, a clay, or a mixture of both (sandclay). For example: s The ability of water to penetrate a soil is a good clue to the soil type. For example, a sand is very quickly penetrated by water, a sandclay is penetrated slowly, and a clay is almost not penetrated at all.
c The consistency of the soil when manipulated in one's hands: fine sand forms clumps
that c m b l e easily, whereas clayey rnatenals typically f o m clumps that are either hard or malleable, but do not c m b l e easily.
c The ease with which the soil is washed off the equipment, e.g. electrodes, plastic
bowls, soil box, rnetal spatulas, etc. Sand rinses off equipment easily, requiring no scnibbiig at all. Clays, on the other hand, require significant brushing to be rernoved, and sandclays are relatively easy to wash off, but notas easily as pure sand. Experience will enable the technician to confidently classifi a soil as a sand, a sandclay, or a clay. The soil types of the samples tested are presented in Table 3.1, in which a sand is represented by S, a clay by C, and a sandlclay by SC.
S o i l# 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 i o i l type SC S S S S SC SC SC S SC S S S S S S S S S S S S C SC C S S SC SC SC SC SC S S SC SC SC SC SC S o i l# i o i l type SC S SC S S S S SC S S SC SC SC C SC SC SC SC SC SC SC SC SC SC SC SC S SC S S S SC S SC SC C S SC SC S o i l# i o i l spe SC SC SC C SC C SC SC SC S S SC SC SC SC SC SC SC S SC S C SC SC S S S S S S C C C SC C S  2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 Table 3...1 Sou Type Results 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 1 O3 104 105 106 107 108 109 110 111 112 113 Il4 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 247 56 ... S o i l# 1 ..
g. and by rollig the soil in one's hands. Again. and distilled water is added slowly to the soil. good drainage by G. Accordiig to PACE. this is a subjective evaluation. a sandlclay Bad: a soil that is almost not penetrated by water at all. The drainage ability of the soi1 is thn classified in one of the following three categories: Excellent : a soil that is easily penetrated by water. and it is dependent on the experience of the technician. The moisture content of the soil is then classified in one of the followingthree categories: Saturated Moist .3. This variable is termed the moisture content of the soil in this thesis. e. humidity refers to the moisture content of a soil on site. humidity is the ability of a soi1 to be penetrated. or as it is received in the laboratory. this parameter is determined very subjectively.g. Drainage Ability The definition of the humidity index in the AWWA Standard is the drainage ability of a soil. According to AWWA. Moisture Content Unlike AWWA.3 Drainage Ability 1 Moisture Content n i e AWWA and PACE standards define humidity differently. e. and poor draiiage by B. The moisture content of the soi1 is determined by visual inspection. the humidity index in the PACE grid is a measure of the moisture content of the soil sample as it is received in the laboratory.g. in which excellent drainage is represented by E. In the laboratory. or to drain water. ïhis variable is referred to as the drainage ability of the roil. e. a clay The drainage ability of the soil samples tested are presented in Table 3. The speed with which the water penetrates the soil is observed. Soi1 is placed in a bowl.2. a sand Good: a soil that is penetrated slowly by water.
percentage of time that a soi1 is saturated. irrespective of the corrosivity of a soi1 in sanirated condition.e. For example. This test should therefore be used in conjunction with interviews with the individuals who are knowledgeable of the condition of the soil in general. i. Knowledge of the moisture conditions that a soil is subjected to throughout the year will enable the engineer to determine how corrosive the soil is to a water pipe placed permanently in that soil. However. and dry. and a saturated soil by S.3. The rnoisture contents of the soil samples tested are presented in Table 3. in which a dry soi1 is represented by D. . if it is kept very dry throughout the year..a moist soi1 by M. the pipe will not suffer any corrosion.Dry ïhis parameter estimates the moisture content of the soil under usual circumstances. moist. the state of one sample does not indicate the general yearround conditions.
2 Drainage Abiliîy Resulis 59 .Xainage S o i# Xainage a e Ability Ability = 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 1 O3 1 O4 105 1 O6 107 108 109 110 111 112 113 114 115 116 117 Ability G G E G E E E G G G E E E E E E E E E G E E B G B G G G G E E E E E E E E E E E E E E B B B B B G G G G G G G G G G G E B G B E E G G G G G G B G G G E G G G E E E E E E B B B G E E E B E E G G E E G G B E G B B B B B E v G G G G  Table 3.
40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 7s 76 77 78 Soi # Table 3 3 Moisture Content ResuItc 60 .
The pH of the soi1 samples was measiued in two different ways. Furthemore. the pH of the soil was detennined accordiig to these two procedures because they were recommended by the AWWA and PACE grids. and were required to calculate the corrosivity index accordiig to each of these grids. This test may better represent the case in which the soil is saturated after a heavy rainfall. The first method consisted oftesting the soi1 in the state in which it was received in the laboratory. an electronic device with a probe that can be inserted into a solution of an unknown pH. . i. i.e. A pH meter is an example of an ionselective. and a potentiometer that measures the potential between the two electrodes. Although both procedures have their limitations in applicability. The second method consisted of testing the soil once it had been saturated with distilled water. or snow melt. or ionspecific. pHsaturated. It is based on the principle that the measured potential of a solution depends on the concentration of the reactants and the products involved in a cell reaction. pHdirect. The pH meter has three main components: a standard electrode of known potential. The potentiometer reading is automatically converted electronically to a direct reading of the pH of the solution being tested.e. it represents the conditions in which the soi1 is found during the linear polarization test. elecirode. a special glass electrode that changes potential depending on the concentration of H 'ions in the solution into which it is dipped. Necessary Equipment pH meter 30 ml plastic container with cap Distilled water The pH was measured using a pH meter. This test serves to represent the conditions found on site.
.5. The pH electrode is simply immersed into the soil and the value obtained is noted once it has stabilized. The pH of the slurry is then determined by immersing the pH electrode into the saturated soil.4. because of the delicate nature of the glass bulb. The mixture is allowed to rest for approximately 5 minutes. PACE recommends thrit the pH of the soi1 be determined by testing a slurry consisting of soil and distilled water. A silver wire coated with silver chlonde is embedded in the solution.151. The 30 ml plastic container is filled halfway with soil and then filled almost to the top with distilled water. and allowing the value to stabilize. Thus the electrical potential vanes with the pH of the solution tested 1'4. The values of pHsaturated of the soil samples tested are listed in Table 3. Extreme care must be taken when attemptiiig to plunge the pH meter into dry clay. The AWWA recommends that the pH of the soil be determined for the soil as it is found in its natural state. or into a soi1 containing small pebbles. The values of pHdirect of the soi1 samples tested are listed in Table 3. The container is then capped and shaken vigorously.The g l a s electrode contains a reference solution of dilute hydrochlonc acid in contact with a thin g l a s membrane. The electrical potential of the glass clectrode depends on the difference in H+ concentration between the reference solution and the solution being used in the test.
9 6.1 6.5 7.1 8.8 8.7 7.1 5.7 5.7 6.8 7.2 7.2 Table 3.6 7.8 7.6 7.7 6.1 6.7 7.1 8.9 6.2 7 7.2 7.1 7.5 7.6 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 Soil # PH PH direct = .3 6.4 7.2 7.7 8 7. 63 7.4 7.6 6.9 6.2 6.9 7.7 6.4 7.3 7.2 7.8 7.4 8 7.3 7.2 7.4 7.4 8.7 7.7 5.8 7.9 7.2 7.7 6.9 7.8 6.7 7.3 7.7 6 5.3 7.Soil # PHdirect direct 6.5 7.9 7.1 6.5 7.4 pHdirect Results .9 7 7.3 7.1 5.6 7.1 6.8 7.5 6.8 7.6 7.9 7.4 8.8 7.8 8.
Soil # Soil # 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 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 Table 3.5 pHsaturated Results 64 .
The voltage on this instrument. is . in which the soi1 is tested as it is received in the laboratoiy to represent the condi:ions found on site. the redox potential is measured in two different ways for each soil sample. this has been accomplished by inserting a variable voltage device. when the current flows through a wire. V. r Digital voltmeter r r 30 ml plastic container with cap Distilled water The oxidationreduction potential is measured using a digital voltmeter. The key to determining the maximum potential is to perfonn the measurement under conditions of zero current. The first method is the direct measurement. The second method involves testing the soi1 once it has been saturated with distilled water. This instrument measures the "driving force" or the "pull" of the soi1 on electron. This potential is the electromotive force (emf) of the cell. The unit of eleclrical potential is volts. i. A traditional voltmeter will therefore measure a potential that is less than the maximum cell potential. powered ffom an external source.3. this variable is required to calculate the corrosivity index according to the AWWA standard. This measurement is referred to as redoxsaturated. in opposition to the cell potential. These electrons would be supplied by the oxidation of an anode placed in contact w i t h the soil.e.5 OxidationReduction Potential (Redox Potential) Like pH. However. redoxdirect. Also. the frictional heating that occurs wastes some of the potentially useful energy of the cell. The first voltmeter measures the potential by drawing current through a wire of known resistance ['4s151. called apotentiometer. This method serves to represent the conditions in which the soil is found during the linear polanzation tests. so that no energy is utilized. Traditionally. metal objects embedded in the soil. and it is a measure of the tendency of the soi1 to corrode a metal.
'51. it may later register a potential above 100 mV. It is essential to keep the soil container well sealed. .7.adjusted until no current flows in the ceIl circuit. the redox value does not Vary above 1 mV per minute. The values of redoxdiuect for the soil samples tested are listed in Table 3. the ce11 potential is equal in magnitude and opposite in sign to the voltage setting of the potentiometer. Le. RedoxSaturated The slurry prepared for pH testing accordiig to the pHsaturated method is used to test for the redoxsaturated value. It has been observed in the laboratory that a soi1 whose redox potential is below O mV. In testing for the redox potential. and is the mnrimum ce11 potential since no energy is wasted in heating the wire. More recently. Redox tests on soil samples were always performed first. The values of redoxsaturated for the soi1 samples tested are listed in Table 3. an attempt was made to limit the exposure of the soi1 to the ambient air. Under such conditions. once left open to ambient air for half an hour to an hour. and this container was closed as soon as possible afier retrieval of the soil sample. These instruments have since replaced potentiometers in the modem laboratory due to their ease of use. The platinum electrode is immersed into the soil. as it is received in the laboratory.6. as soon as the container of soi1 was opened. and the redox value is noted once the value has stabilized. The platinum electrode is immersed into the sahirated soil. RedoxDirect The AWWA recommends that the redox potential be determined for the soil. and the value of the potential is noted once it has stabilized. such as the one used in this project. to ensure that the readiig taken is not affected by the exposure to the oxygen in the air. advances in eleckonic technology have allowed the design of the digital voltmeters. that draw only a negligible amount of current [14.
Redox 7 Redox Redox Redox direct direct Soi # direct (mv) (mV) 214 3 8 150 184 178 118 175 191 219 232 200 183 180 200 220 23 1 203 210 20 1 224 3 3 64 178 240 134 14 38 219 194 144 112 4 1O 164 170 154 187 192 214 169 (mV) 209 208 220 194 181 216 204 263 216 200 210 183 21G 49 132 185 208 81 228 228 274 260 228 219 228 185 193 171 155 175 190 147 121 183 229 180 260 225 218 (mv) 160 230 230 184 190 50 237 281 320 156 192 208 190 185 197 181 167 188 180 147 178 148 191 219 165 195 189 155 139 150 130 246 247 154 28 217 direct 67   Table 3.6 Redoxdirect Results .
7 RedoxsaturatedResulis = .Redox 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 26 27 28 29 30 31 32 33 34 35 36 37 38 39 Soi # aturated (mv) 196 188 225 168 258 194 252 256 218 198 153 165 149 121 140 156 176 186 180 214 264 229 163 191 206 187 179 162 155 154 171 111 155 165 226 115 270 204 197 Soi # Redoxidhnated (mv) 206 197 223 80 187 40 262 267 167 134 175 188 191 180 190 173 159 177 145 174 183 188 193 205 136 161 185 128 99 112 152 225 230 93 15 222 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 247 68 Table 3.
p. Soil box Ohmmeter Four wires with clamps at both ends The resistivity of a given object is calculated by making use of the relationship between resistivity. The second method is to measure the resistivity of the soi1 once it has been saturated with distilled water. is directly proportional to its length and inversely proportional to its crosssectional area. on the other hand. is the property of a body or mass with discemible geometry. when the soi1 conductivity is at its highest. pdirect. copper. The first method involves measuring the resistivity of the soil as it is received in the laboratory. e. The lower the resistivity.g. R. The resistivity of a soi1 is measured in two different ways. Both measurement are necessary to calculate the corrosivity indices according to A W 7 Aand PACE. While resisîance is a function of geomeby.6 Resistivity. The latter represents the worst case. In other words. The following equation shows the relationship between these variables .g. has a significant influence on the rate of corrosion of a metal exposed to it. or a specific soil. The types and the amounts of the various dissolved salts in a soil. psaturated. when measured between parallel faces. Resistivity. p It is found that the nature of the electrolyte.3. The resistance of a recîangular body of any substance. or a block of soi1 of a given size. the more the electrolyte contributes to corrosion. Resistance. is a characteristic property of the material. particularly those which ionize most readily. resistance and geometry. resistance decreases. are estimated by measuring the electrical resistivity of the soil. e. a piece of wire. in this case the soil. resistivity is not dependent on the geometry of the body Il1. as the depth and width increase.
The soi1 box is a rectangular box with an open top. i. such that the values of W. The box is filled to the top with soil. what is actually being measured is R. R is measured using a soi1 box and an ohmmeter. p. made of a nonconducting material (usually plastic) wiîh metal ends and two metal pins inserted into the side of the box ['l. l i s represents the woet possible case. and p is then calculated using Equation 3. is then calculated automatically and displayed by the ohmmeter. when the conductivity of the soil is a maximum. A suficient quantity of soil is placed in a bowl. and distilled water is added gradually in small quantities. n i e value of R is then calculated according to the following relationship ['l: The value of the resistivity.1. and the current is introduced by means of the two end plates ani the potential is measured across the two pins. psaturated The AWWA method suggests that the resistivily of the soil be determined when the soil is saturated.where R = the resistance of the rectangular body (Ohms) p = the resistivity of the substance making up that body (Ohmcm) W = the width of the body (cm) D= the depth of the body (cm) L =the lengtli of the body (cm) When measuring p. The soil and water are mixed continuously to encourage .e. It is then connected to the ohmmeter. and L are known. D.
the wet or dry soi1 is added to the soil box and compacted. and extreme care must be exercised when adding water to avoid supersaturating the soil. and to ensure uniformity and reproducibility of the measurement. The box is then wired to the ohmmeter. . as they will result in higher values of p. will be absent fiom the soil box. which are found in this excess water and which give the water its conductive properties. which will not be tmly representativeof the soil's ability to conduct ions. The values of pdirect for the soil samples tested are listed in Table 3. Some expenence is needed to ensure that the soi1 has reached saturation. where it is compacted well to eliminate any air bubbles or voids. the soil is tested for resistivity in the state in which it is received in the laboratory. the excess water may separate 6om the body of soi1 and it will not be transferred to the box with the rest of the soil. According to the PACE method.9. Ions such as chlorides. Therefore. When the soi1 is saturated. and the reading is taken. it is transferred to the soil box a linle at a t h e . air bubbles must be absolutely avoided.penetration of the water into the soil. The values of psaturated for the soi1 samples tested are listed in Table 3. Once more. When a soil is supersaturated. and a readiig is taken. This will result in a higher rcsistivity. The box is then attached to the ohmmeter.8.
2 102.Pahnated )hmsm: 1947 1377 7410 1571 1888 1417 2623 2181 2211 2359 3060 5980 5140 2625 250 87.9 1838 5780 6490 2309 4800 4720 11000 8220 34400 18310 9370 17150 3070 2589 2523 1572 2135 2269 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 247 228 190 780 165 5300 4330 4770 2343 2097 1834 1284 1856 2396 1748 3580 367 6 1400 409 132600 5820 4020 90800 299 4080 3650 4960 3200 778 682 613 2076 1008 1112 1706 1040 2890 1591 2685 2275 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 Soi # Soi# Pahnated  Table 3.6 81.8 p saturated Results  ePha  .
3 1482 1736 841 496 4000 2012 8230 67900 26970 40200 120700 77200 6040 11930 4080 8900 1247 2980 62100 44700 10440 6040 9040 61800 14960 16610 11230 3830 1389 2121 2688 1131 2159 7140 1504 2078 1790 2064 623 146700 224.Sol# direct ( 0 1 280 228 1592 173 5300 4340 4780 2277 1940 1713 1223 1904 3550 1813 3580 1443 101300 833 220800 5820 180000 309 18570 3840 13820 10580 825 707 723 2235 1311 1568 3830 1210 7750 2593 10870 3210 P P Sol# 3820 1410 9280 12550 31800 1987 2198 4120 direct ohm@  direct ohmcm: 4100 3170 2218 82400 P   ohmcm: 1947 1683 13300 1577 5140 1429 3750 4400 7600 4850 90100 13360 27180 42000 iO58 568 779 28 1.8 2449 7340 1901 8240 2599 73  Table 3.4 5000 151800 7490 22340 16230 37600 27860 40900 30400 35100 3860 3460 2612 1548 2032 3870 direct P 1 2 3 4 5 6 7 8 9 IO 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 4 4 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 9460 129300 1943 1618 1247 1205 3820 3220 5660 3140 3160 1271 205.9 p direct Results .
the soil is considered to undergo a violent reaction. The first method uses a solution of iodiie and 3% NajN. and the second a solution of HCI along with a strip of Ieadacetate paper. If only a slight sound can be heard (or none at all). Eauioment c 2 standard test tubes c Concentrated HCl acid (15%) A strip of lead acetate paper % A solution of 12 (aq) + 3% Na3N The AWWA procedure for testing for sulfides is to saturate a small quantity of the soi1 with a solution of iodine and 3% Na3N. and may be quite subjective. and to observe the resulting reaction. Although only visual observation is recommended by AWWA. or absent. The mixture is then shaken well.3. This is because the reaction is never very violent. sound was also used to help distinguish between a violent and a normal reaction.7 SuIfide Content The sulfide content of the soil is determined in two different ways. A mal1 amount of soi1 is placed in a test tube. and it is ofien difficult to differentiate between the degrees of reactions. These two methods were chosen because they were recommended by AWWA and PACE. especially between the normal and the violent. This test is a qualitative one. and the degree of reaction is obsewed and classified as either violent. normal. and bubbles c m be seen. NecesSan. If bubbles can be heard to be exploding at a quick pace. and are required to calculate the corrosivity indices. then the soil is classified as reacting . and the iodine solution is poured into the test tube to top the soil.
and the test tube is then covered at the top with the thumb of the tester. where N represents no sulfides. The bubbling is the result of the formation of hydrogen gas. it is highly recommended that one avoids breathiig il. as determined by AWWA. However. T represents traces of sulfides. if no reaction was obsewed. The mixture is then shaken gently. then the soi1 was assumed to contain no suifides. in which N represents no sulfides. and care is taken not to wet the indicator paper. HCI and Lead Acetate Paper PACE recommends using concentrated HC1 in combiiation with lead acetate paper to determine whether the soi1 contains sulfides. the paper is obsewed for signs of a brown discoloration. The sulfide contents of the soil samples. and then 15% HCl is added to top the soil. then the sulfide content of the soi1 was assumed to be high. that this experiment be carried out under a fume hood. are presented in Table 3. as this product is extremely toxic. Ifthe reaction was classified as normal. Fially. AAer a couple of minutes.normally. A strip of lead acetate paper is introduced and held at the top. The degree of the reaction was then used to establish the sulfide content of the soil. and P represents the presence of sulfides. When the acid is added to the soil. Any discoloration indicates the presence of sulfides. characteristic of the H2S gas. and a lot of bubbling. it is very common to observe a violent reaction. Only the discoloration of the lead acetate paper can correctly determine whether or not sulfides are present. then the soi1 is assumed to contain no sulfides at all. If no bubbles are seen or heard. This may be the result of the reaction between HCI and any carbonates that may be present in the soil. and that the room be kept well ventilated or. better still.10. and P represents the presence of sulfides. A small amount of soi1 is placed in a testtube. usually present along the edges of the paper.1 1. If the reaction was classified as violent. then the soi1 was assumed to contain traces of sulfide. The sulfide content of the soi1 samples. are presented in Table 3. and does not indicate the presence of sulfides. as determined by PACE. . Another indication of the presence of sulfides is the smell of ronen eggs.
10 SuIfide Content Results Usiug Iodinc Solution  76 .Suifide content ?due) N T N T N P = Sulfide content &xüne) T T N N N N N N T T N N N N N N N N T T P P N T T P P N T T P P N N N T Suifide content 5odine) N T N N N N N N N N N T N P P N N N N T N N N N N P T P N N N P N T N T N N N = Soil # Suifide content riodine) N N P P P P P  118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 747 T T N P N T N P P P P T T T P T T P P P T T N T T P P P P T P P P T P N N T N N N P P P P N N N N N N N N N P N N N T T T  T P N Table 3.
.
8 Chloride Concentration The test for chlonde content is not a part of either the AWWA or the PACE procedures.1 Necessaw Equioment Potentiometer Chloridespecific electrode Electrode wening agents.3. and the rccorded value is compared with the pretabulated values to obtain the chlonde ion concentration of the solution. p. The overall procedure can be summarized as follows: The sample is dried and pulverized. pH. The mixture is allowed to sit ovemight. The potential of the solution is recorded with a chlondespecific electrode. The chloride concentration of the soil itself is then calculated. permitting the iÏee C1' ions to enter into the water. The finest particles are kept and combied with distilled water. i. solutions of 1M (PJH4)2S04or 1M KNOJ 8 Ceramic bowl and hammer 30 ml plastic containers 2 mm and 200 pm sieves 200 ml beakers 8 8 Microwave oven Scale Powdered KCl Distilled water Jcloth + an elastic band Stop watch a . redox potential. etc.8. It is one of the goals of this project to determine if knowledge of the CI. Le.ion content would permit us to evaluate the corrosivity of a soil better than it could be determined if only the other parameters were known.e. 3.
ions only 114. 3. An example of an ionspecific eleckode is the pH meter discussed in Section 3. The soil is then passed through a 200 pn sieve. i.e. i. When the soil has cooled suficiently to permit handling.151. . Extreme care must be exercised when handling the beaker as it reaches very high temperahues. Glass electrodes can be made sensitive to ions such as Na'.4. It is based on the p ~ c i p l that e the measured potential of a solution depends on the concentration of the reactants and the products involved in a ceil reaction 1'4. If the quantity is insufficient. of soils in the tarred container is recorded. The sarnple is dried in a microwave at a high temperature for 35 minutes. The container is then capped. and CI' by changing the composition of the membrane. Approximately 5 g of soi1 should be recuperated. or as long as necessary to thoroughly dry the soil. The exact weight. but m u t be obtained through a series of steps which are discussed in the following sections. The recuperated fine soil is then rehmed to the bowl where it is pulverized further to a fine consistency. and shaken vigorously for 30 seconds. The soil is pounded with a hammer for a few minutes to separate any larger pebbles from the fmer soil.1. ï h e sample is then allowed to sit ovemight. the above procedure can be repeated until such an amount is retrieved. and distilled water is added to the soil in a ratio of 2:1. some of it is kansferred to a ceramic bowl. a CI' ionspecific electrode was used to determine the potential resulting fiom the presence of Cl.8. an electrode that is sensitive to the concentration of a particular ion. the potential is not converted automatically. In this case. 10 g of water are added to 5 g of soil. and the soi1 recuperated is ûansferred to a clean.151. and covered with a piece of Jcloth which is secured in place with an elastic band. The pulverized soil is passed through a 2 mm sieve to remove the pebbles that cannot be pulverized. Unlike the pH meter. tarred 30 ml plastic container. N I & ' . K'.The chloride ion concentration is calculated indiidly fiom the potential that is measured using an ionspecific elccirode. in grams.e.2 Samvle Prevaration A 200 ml beaker is filled half with soil.
or a commercially prepared wetting agent of unknown composition.12 shows the weight of KCl to be added to 1 kg of distilled water in order to obtain the desired concentrations. These solutions are prepared by simply adding KCI. Solutions of 0. 0. 0.12 Preparation of Csiibrating Solutions . which is sensitive to C1' ions only.3% CI' ions are required.The potential of the previously prepared sample is recorded with the aid of an ionspecific electrode. The choice of wetting agent appears to make no difference in the final results.03%. When the electrode is ready.8. as well as the equivalent concentration in ppm. care must be exercised to enswe that no air bubbles are present in the wetting agent.4 Pre~aration of Calibratine Solutions In order to calibrate the electrode. or NaCl crystals to distilled water in the correct quantities such that solutions with the desired concentration of CI' ions are obtained. the potential of different solutions of known CI' concentrations are recorded. and filled with a wetting agent.  Table 3. W s electrode.01%. When filling the electrode. 0. The electrode is rinsed thoroughly with distilled water. 3. and 1. registers the potential of a solution due to the presence of only the Cf ions.33%. Table 3.65%. when atîached to a voltmeter. it must then be calibrated using solutions of known chlonde ion concentrations. . 1M (NH&S04. The wetting agents used in these expenments were 1M KN03.
0.6 Calibration Curve and Eauation ï h e calibration curve is constructed fiom the potentials registered for each of the five calibration solutions. 0. 3.03. and 1. The electrode is placed into a solution.3. the electrode is calibrated. calibration is complete. 1 minute is usually sufncient. is presented in Appendix B. A calibration c w e .01. An exarnple of the potentials obtained during one calibration exercise are given in Appendix B. .5 Calibration of Electrode Once the calibration solutions and the electrode are prepared. This curve. The values of the chloride ion concentration (%) are ploned against the average potential values. fiom the most concentrated to the least concentrated solution.65. and must remain the same for al1 subsequent readings. For each solution (0. and an exponential c w e is fined to the five points.g. Further measurements are then taken until reproducibility of the potentials is obtained. If the potentials are approximately equal. along with the correspondiig equation. along with its equation.8. then the electrode should be checked closely for any problems such as the presence of an air bubble in the wening solution of the electrode. and the technician is confident of the results obtained. will be used to obtain the C1' concentrations of the solution of the samples.8. If the values Vary significantly.3 % Cr)the average potential is calculated. This time must be chosen pnor to taking the fmt reading. and then in random order. and the reproducibility of the potential is determined. Each of the five calibration solutions are tested in tum. but 3 minutes may be needed to achieve stability of the reading. e. etc. the lack of wetting agent due to a leak. This is done by altematively reading the potential of each of the calibration solutions. Each solution is tested twice. In order to avoid contaminating the calibration solutions.33. the electrode should be rinsed with distilled water and tapped dry before taking the next readiig. 0. and held upnght for a predetermined amount of time.
The calibrated electrode is lowered into the 30 ml container.000. or by calculating it using the calibration equation.13. and the potential of the solution is registered. and not in the liquid fiaction of the prepared sample. it must be transformed into a value more intuitively understandable: percentage concentration. Soil Samales The samples prepared the previous day are now ready to be tested. although the concentration in % could have equally been used.8 Determination of Concentration of Chloride Ions of Soil Once the potential of the liquid fiaction of each sample is obtained. The values in ppm are retained for further data analysis. The electrode is then held upright for the tirne chosen during calibration (13 minutes).8.3. 3. This is very easily.8. An example of this is s h o w in Appendix B. The mixture of soil and distilled water has now separated into two parts. given that the standards indicate that 26 hours are sufficient to allow al1 C r ions to enter into the distilled water. is obtained by multiplying the concentration in percentage by 10. Care must be taken not to disturb the settled layer before testing the liquid part. in ppm. The chloride ion concentrationsof the soil samples are presented in Table 3. until the membrane at the tip is fully immened in the solution liquid above the precipitate. or ppm of C r ions. and quickly done by readiig off the concentration value in percentage terms fiom the calibration cuve. and the deposited soi1 particles. The variable of interest is the concentration of CI' ions in the soil. .7 Testine. Finally.ions. the concentration of Cf ions of the soil. This value is obtained by simply doubling the concentration of Cf ions in the liquid fraction. The liquid part contains the Cl. This is due to the fact that a ratio of 2:l between the water and soil weights was used during the sample preparation.
Ciment CI CI @PI @Pm) Soi # :ontent Soi # :ontent Soi # @ P ) 243 347 59 160 282 310 268 419 328 258 125 52 34 82 9223 13652 22664 17754 759 75 53 29 149 30 30 28 14 26 72 47 95 154 155 73 35 1042 Table 3.13 Cbloride Ion Concentrations 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 80 1835 155 168 81 2310 4592 1094 249 436 38 46 58 77 54 81 148 111 148 716 345 3257 123 758 448 2030 537 391 423 160 380 1345 7161 12556 210 56 407 36 157 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 1O7 108 109 110 111 112 113 114 115 116 117 172 190 222 17 5 O O 6 3 51 362 283 272 253 142 207 81 22 1O9 265 5294 326 320 2067 5394 481 2712 340 191 42 1 1830 756 233 65 17 9 28 759 374 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 247 Ce  83 .
along with the reference and the auxiliary electrode. and encourages corrosion engineers to depend on corrosivity indices such as those proposed by AWWA and PACE. a A reference electrode: the CuICuS04 electrode which measures the potential of the working electrode at any point during linear polanzation. and which acts as the electncal conductor between the anode and the cathode. The result of this test is the corrosion rate. . and that requires a very expenenced technician. linear polarization is a test that is t h e consuming. and the corrosion rate is obtained from Tafel and polarization resistance diagrams. The surface of the metal specimen (working electrode) is prepared according to a specific procedure and immersed into the saturated soil. in d y r . An auxiliary electrode: the graphite rod which plays the role of the anode in cathodic a polanzation. Although very informative and precise. that the steel sample will undergo in the given soil. The corrosion ce11 set up is made up of the following elernents: a A working electrode: the steel specimen which plays the role of the anode during anodic polarization. Al1 this makes the test generally inaccessible. and a The potentiostat which controls the potential of the system.3. the equipmeni is quite expensive. Furthemore. The electrodes are wired to the potentiostat. The procedure for testing the soil samples can be summarized as follows: the soil sample is saturated and a glass jar is filled up to a specific height with the saturated soil. and the cathode in anodic polarization. which can be calculated ftom the results of very simple and inexpensive tests. . An ionic conductor: the saturated soil sample which allows ions to travel fÏom the a cathode to the anode.9 Linear Polarization The final test is the h:ar polarization of a standard steel sample exposed to each of the soil samples. and the cathode during cathodic polarization.
This halfce11 reaction is the reduction of CU" ions: In order to obtain the potential against the standard of hydrogen ion reduction. It a a s created 6om material cut 6om a ductile iron pipe removed 6om the ground for testing by the .1 Necessarv huioment Potentiostat: the CMSlOO Elecirochemical Measument Çystem by Gamy.3. and specimen mount A hand drill and support No. Graphite electrode (auxiliary electrode) Cu/CuS04 electrode (reference electrode) Standard metal specimen. For example.000 V by convention). This means that. the potential is measured against the reduction of copper ions.400 V Vs CU'+ reduction . 200 and 400 sand paper 1. cu2+. Regardless of which electrode is chosen.9.2 mm and a diameter of 9 mm. a potential of 0. The standard metal specimen used in the expenments consisted of a small cylinder with an approximate height of 14. electrode. the value of 0. it is used to measure the potential of the working electrode at any given time during the experiment. agglomerate6ee.O micron.337 V is subtracted fiom the value of the potential obtained against the CuICuS04 electrode. which consists of metallic copper immersed in a solution of saturated copper sulfate.063 V against H+reduction. instead of measuring the potential of the system against the standard of hydrogen ion reduction (whose potential is 0. alpha alumina powder by Leco Acetone Caliper Glass jar The reference electrode used was the CdCuSO. Inc. is equivalent to a potential of 0.
. such that it could be screwed onto the erid of a rod.". To identify the method of preparing the surface of the steel specimen.1 Componcnts of the Working Elcctrode 3. is in constant contact with the potentiostat. because if the technician is unable to perform the test in a repeatable manner within a prescribed tolerance. 1 . to the potentiostat at the other.6 Rod I Steel Specimen Figure 3.'. This wire ensures that the steel specimen...a. to poentiostat  ".authority of COREXCO..9. Figure 3.1 shows a schematic of the working electrode made up of a steel specimen screwed onto the rod. This process is very important. then the result would be unreliable. Montreal. trial u s were performed on expendable soi1 samples to determine the exact procedure to be followed such that reproducibility of results is ensured.. which is later immened into the soil.. The specimen was machined in the Civil Engineering Materials Testing Laboratory.2 Trial Runs and Reproducibilitv of Kesults Before testing any of the soils that were retained for further analysis. It \vas fomied w i t h a "thread" m i n g through the center. This rod consists of a long thin tube through which runs a wire comecting the metal specimen at one end. The trial runs served the following purposes: To identify the method of preparing the soi1 samples.
then the same area of graphite will be in contact with the soil. The complete procedure was 0 established and is presented in the following section. . and the height of the soi1 is always the same. it eliminated one of the variables that differs between the samples. Care must be taken not to ovenaturate the soi1 because the conductive properties of the soi1 may be incorrectly estimated if the excess water bleeds to the surface of the soi1 during the polarization testing. From these results. i. i. which is filled to a specified height.e. it can be seen that the procedure established yielded reproducible results to a satisfactory degree. Trial runs were performed on three different soils. The soi1 sample is tested under conditions of saturation. it is transferred to the mason jar. until the soil is saturated. It should be noted that. and distilled water is added gradually in small quantities. To determine the scan rate and the scan range to be used in obtainiig the Tafel and polarization resistance diagrams. constant cathodic area. Furthemore. moisture content.0 To provide the technician experience and the ability to perform the tests quickly and consistently. and worked into the soil. which consists of the area of the graphite rod which is in contact with the soil.e. The height requirement is intended to ensure reproducibility of the cathodic area. if a soi1 is completely dry. Soi1 is placed in a bowl. 123 are presented in Appendix C. If the graphite rod is immersed into the soil such that its end touches the bottom. and To determine the time to be provided for the steel specimen to stabilize in the soil pnor to polarization. linear polarization of the steel specimen is not possible because the system is missing a key element: the ionic conductor. The results of the trial run performed on sample No. Once the soil is saturated. The soi1 is saturated in order to represent the worst case scenario in which the soil's conductive properties are highest.
the presence of a protective surface film would result in a lower corrosion rate. and then with the sue 600 paper.l proceed. As observed previously. it can greatly affect the rate at which the corrosion w". the specimen must be prepared in a consistent manner each time to ensure reproducibility of the results. which ensures a smooth preparation of 1. i. When a tight seal is ensured. the actual anode area will be smaller than what has been assurned.9. it is sanded on al1 sides with the size 400 paper first. if the steel specimen is in contact with an air bubble. Two sandig papers are used: sizes 400 and 600. the steel specimen is polarized four times. then the results obtained would be rnisleading. For example. 3. For this reason. The steel specimen is prepared next. and therefore the corrosion rate will be underestimated. whose diameter is compatible with that ofthe steel specimen thread. an ordinary hand drill is mounted securely on a stand and a screw.The soil must be observed for signs of air bubbles. As the drill rotates the specimen. The steel specimen is then secured onto the end of the screw. Lightly shaking the jar may consolidate the saturated soil and eliminate any air bubbles. For each soil sample.e. which tend to increase the overail resistivity of the soil. The surface must be prepared thoroughly pnor to each of the tests. and then Mise with distilled . or if the steel sample is exposed to ambient air after cleaning such that a protective film is allowed to form prior to testing.4 Pre~aration of the Workiie Elechode This section serves to outline the method of preparing the surface of the specimen prior to each polarization sequence. If such a film is not properly removed. and screwed onto the end of the working electrode rod. The soil sarnple is prepared first and the reference electrode and graphite rod are secured into place within the mason jar. surface preparation plays an extremely important part in the corrosion process. the specimen is rinsed thoroughly with acetone to eliminate any greases. is inserted into the "nose".The specimen is then removed fiom the drill. The specimen is then sanded with alumina paste. In order to obtain a uniform sanding. The first step in the surface preparation is the sanding of the surface. Furthemore.0 p.
P. The potentiostat used enables the technician to introduce the desired values of the scan rate.5 cm2(subject to change) Table 3. The goal of this test is to obtain the Tafel diagram.017 mVls (1 mVlmin) Anodic area. metal surface area approximately 4.14 Values Specilied for Tafel Test Once this test is cornpleted. are obtained by plotting the anode and cathode lines such that their slopes coincide with the dope of the Iinear Tafel regions. 3. a graph such as that illustrated in Figure 3. and to extract fiorn it the values of the Tafel constants. and P.e. the scan range. The specirnen is then quickly immened into the saturated soil sample.5 Polarization of the Steel Soecimen Once the soil sample has been prepared and the working. and Pa.water.2 is obtained. auxiliary and reference electrodes have k e n immersed into the soil.9. and the appropriate test is m. The values of P. etc. . the first of the four polarization tests is initiated. Eoc Delay provided to attain E. i. The following variables were specified: i 250 mV fiom Open Cicuit Potential. IR drop compensation 1000 s or 0.
i. are obtained. Eoc 1000 s or 0. EOC 4 M W 7 S V h452lin2 E b 707g*uixO 27'RvEpur C W B m OFF D*ON Km* Figure 3.Taiei C u m 'jk96tfdtan 2Wl199512 10 20 PM*. ï h e following variables are introduced into the program prior to polarization: Delay provided to anain E.87 g/cm' 27.92 g Table 3.0 17 mVls (1 mVlmin) On approximately 4. The specimen is then inserted into the soil again. IR &op compensation Anodic area. and the second test is initiated with the goal of determinimg the corrosion rate of the steel sample by the method of linear polarization.15 Values Specilied for Linear Polarhtion Test 90 . metal surface area Density of metal Equivalent weight of metal f 20 mV 6om Open Circuit Potential.5 cm2(subject to change) 7.2 Typical Tafel Plot Once the values of p.e. and p. the steel specimen is removed from the soil and cleaned accordiig to the standard method.
3 Typieal Linear Polsrizatioo Curve  . a curve such as that illustratcd in Figure 3. the saturated soi1 is discarded and the entire process is repeated a second time with a îtesh sample of the same soil. and p . and the two tests are run again to obtain new values of p.3 is obtained. 96. The values of the corrosion rate for each of the soi1 samples tested are presented in Table 3. n i e value of %. Once the corrosion rate is obtained. Table 3.17. IO. and the corrosion rate are obtained by plotting a line whose dope coincides with that of the line in the region imrnediately sunounding the point on the curve at which the current equals zero. I Figure 3.16 gives the values obtained for soi1 sample No.Once the test is completed. The results obtained indicate that the procedure followed yielded reproducible results. n i e soi1 and the steel specimen are prepared according to the specified methods. and then the corrosion rate.
914 2.970 Eoc 4... i .1 8. .Linear Polarization I 851 852.16 Results Obtained for Soi1 Ssmple # 96 . (mV) (mv) (A 106A/cm2) (A 1043 ohm c d ) % Table 3. .
17 Corrosion Rates .Comsi01 Rate (90 Table 3.
and E.4 shows the spreadsheet used to calculate the corrosivity indices according to AWWA and PACE. and the corrosivity indices are given automatically in lines D and G. . Figure 3.3. and reviewed in the previous sections of this chapter. The values of the appropnate variables are entered in lines A.10 Calculating the corrosiviîy indices according to AWWA and PACE The defmitions of the variables included in each of the corrosivity gids have k e n discussed in Chapter 2.18 and 3. This section introduces the spreadsheets used to obtain the corrosivity indices quickly and without error. The corrosivity indeces of the soils are presented in Tables 3. C.19.
lightbrow METHOD 1: AWWAC105 * I f h pH is b e w n 6 .4 Spreadshnt Used for Quick Calculation of Corrosivity Indices 95 .0 0.ANALYSIS OF SOIL CORROSIVITY SOIL SAMPLE: JK33 On'gin: Dale: Descn'p(ion: St€anvtpot#lO WC6195 Siltyclay.0 INDEX IF 170.01~ Figure 3. 5 a r d 7.add 3poim: m c METHOD 2 : PACE Boalvsls &2h E 1 8 1.0 1.5.ard sulides are preçentandlorthe redoxiç negadve.
18 CorrosMty Indices According to AWWA . AWWA index Table 3.
Table 3.19 Corrosivity Indices According to PACE .
). It was the objective of this study to derive the relationships of the other variables with CorrRate. Furthermore.CHAPTER 4: ANALYSIS OF EXPERIMENTAL RESULTS AND DISCUSSION 4. This variable is denoted 'CorrRate'. 3. obtained by testing a portion of soil supenaturated with distilled water (discrete). n i e analysis consists primady of regressing the variables. Furthermore. and it is recomrnended that Appendix D be consulted pnor to readiig this chapter. Appendix D: Principles o f Regression Anabsis is included for the information of the reader. pHdir: pH of the soil. 2. obtained by testing the soil in the state in which it is received in the laboratory (discrete). Reddir: redox potential of the soil. pHsot: pH of the soil. obtained by testing the soi1 in the state in which it is received in the laboratory (discrete). seven discrete and five categoncal: 1. This data was presented in Chapter 3.1 Analysis of Preliminary Data n i e statistical package SAS was used to analyze the data collected during the experimental phase of this project. individually and in combiiation. the importance of the chlonde content of a soi1 is evaluated. and it is considered to be the "bue" corrosivity of a soil. . with the dependent variable. in mV. The dependent variable 01) in the analysis is the corrosion rate obtained by the method of linear polanzation. There is a total of 12 independent variables O(. both individually and in appropriate combiiations. Once the relationships between the variables is understood. and a decision is made on whether or no1 this variable provides suficient information to be considered significant. the information presented in this Chapter is selective and consists only of the material deemed to be essential.
7. In the majonty of the cases. in mV. only 10 will be used in this analysis. Chl: chlonde ion content ofthe soi1 in ppm (discrete). One of the two variables is therefore redundant. R e m : redox potential of the soil. 11. G for good. M for moist. Furthermore. Drainage will not be included in any of the following analyses because the information it provides is alrnost identical to that of the variable Soilfype. obtained by testing the soil in the state in which it is received in the laboratory (discrete). Drainage: categoncal variable representing ability of the soil to 'drain' water (E for excellent. As a consequence. 10. in ohmcm. the SulfHCl value is unavailable for many observations. 8. 6. and 12. once it had been saturated with distilled water (discrete).4. The analysis of the data is divided into the following sections: Data Exploration Transformation of Variables . and C for clay). a sand will have an excellent drainage ability. and B for bad). SC for sandklay. Ressat: resistivity of the soil. Soilfype: categoncal variable representing soil m e (S for sand. in ohmcm. and a clay will have a poor drainage ability. and this results in a decrease in the reliability of the results of the statistical analyses obtained using this variable. 9. the variable SulfHCl will also be eliminated fÏom the list because it is felt that errors were made during testing for this parameter. 5. and P for positive). and S for saturated). Resdir: resistivity of the soil. Sul'CI: categorical variable representing sulfide content obtained by testing the soil using concentrated HCI and lead acetate paper (N for negative and P for positive). Of the 12 variables. a sandlclay will have a good drainage ability. Stilfl: categoncal variable representing sulfide content obtained by testing the soi1 using a solution of iodine and Na3N (N for negative. obtained by testing a portion of soil supersaturated with distilled water (discrete). Moisture: categoncal variable representing moisture content of the soil as it is received in the laboratory @ for dry. and it was decided to retain the variable Soilfype. T for trace.
the following information is extracted fiom SAS output files. and they must be identified and observed during the course of the statistical tests that follow. Furthermore. and the skewness.1 displays the information produced by SAS for the variable pHdir.Regressing Discrete Variables One At A Time Correlation Matnx RSQUARE Procedure Includiig Categorical Variable Variables Retained for Further Analysis Determining Sigiificance Discussion of Results 4. skewness.(N). outliers.1. and The outliers. and the normal distribution plot. The five quantiles. The stem and leaf diagram. includig the stem and leaf diagram. etc. the standard deviations. Each of the eight discrete variables is studied individually and the distribution of the values are observed for signs of normality. For each variable. and examined: a The number of observations. the box plot. the variance. the box plot and the normal distribution plot. the mean. a a a a Figure 4. The five highest and five lowest observations. The distribution of the data plays a very important role in ensuring that the results of regression analyses are consistent. the range and the h i g e spread. outliers are also very influential.1 Data Exaloration The first step in any analysis is the familiarization with the experimental data. .
the data points seern to be well distributed and the box plot appears to have a standard shape. This indicates a small deviation fiom normality. with a relatively good box plot. Besides the outliers. but a slight deviation fiom normaliîy is still . the box plot and the normal distribution plot.The pHdir values range between 4. in fact it appears to be slightly curved. the normal distribution plot is not exactly linear. Besides the outliers. There are seven outliers: one in the upper end. Figure 4. including the stem and leaf diagram.8. The usefulness of a transformation is exmined in the next chapter. This generally indicates the presence of outliers in the lower end of the distribution. observable. The pHsa! values range between 4. with four outliers in the lower end only.2. i.e. and six in the lower.7 and 9. As withpHdir. and this is quite evident when the stem and leaf diagram and the box plot are studied. the data are slightly negatively skewed. the data seern to be well distributed.2 displays the information produced by SAS for the variable pHsur. the mean is slightly smaller than the median. n i e normal distribution plot is a linle less c w e d than that ofpHdir. Fially. The data are slightly negatively çkewed.2 and 8.
.
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However. it cannot be concluded form the above test that the data set is normally distnbuted. the box plot. the remainimg variables tend to be lumped together.5 f 30. Figure 4. A clue to this can be drawn from the observation of the quantiles. the three extreme values are removed and the process is repeated. includig the stem and leaf diagram.8 mV are 218. This indicates a deviation 60m normality which may be corrected by a transformation in the next section. This is a somewhat high number. The values obtained by 187.Reddir Figure 4.5 mV. In order to determine the normality of the vanable. This may not be the case. and therefore. includig the stem and leaf diagram. aside from the outliers. in fact it is significantly curved. with 13 outliers in the lower end. the box plot and the normal distribution plot. and as such. The presence of these three observiitions force the diagrams to be drawn with large intervals. Dividing this value in h o . This is characteiisticof the symmetnc normal distribution. If the extreme values are ignored and only the values withh the hiige range are examined (behveen 4 3 and QI). the data points are well distributed and the box plot appears to have a standard shape. It may appear from the various diagrams that the situation is unacceptable and that the distribution is not at al1 normal. These values are very close to the actual ones of 216.3b displays of relevant information.7 mV. However.3a displays the information produced by SAS for the variable Reddir. 138 and 320 mV) may be the cause of the box plot and the normal distribution plot having such a distorted form. an equal number of observations are noted to be above and below the median. In this case. gives a values of 30. The very large extreme values (528. the normal distribution plot is not quite linear. . and the normal probability plot for Reddir without the three extreme values. For a normal distribution. The data are slightly negatively skewed. Fially. the values obtained by adding and subtracting this value from the median will correspond approximately to the values of 4 3 and Q1.8 mV.3 mV and 156.5 mV and 155 mV. the hiige range is equal to 4341 = 61. the variables are well distributed within the hinge area. The Reddir values range between 528 mV and 320 mV.
.
.
the box plot and the normal distribution plot. When this value is removed and the process repeated. In this case.5 mV and 144.Rebat Figure 4.4b. The Rebat values range between 475 mV and 282 mV. the data points are well distributed and the box plot appears to have a standard shape. aside fiom the outliers. Fially. However. with the outliers in the lower end.5 mV and 174 i 29. the normal distribution plot is fairly linear. it appears that the cause of the distortion in the diagrams is the one extreme value of 475 rnV.5 = 206. The data are slightly negatively skewed.4a displays the information produced by SAS for the variable Rebat. This indicates a slight deviation from normality. ïhese values are quite close to the true values of 196 mV and 137 mV. However. This was the result anticipated. Once more. The results obtained are presented in Figure 4. the resulting boxplot and normal distribution plot are greatly improved. including the stem and leaf diagram. an examination of the quantiles results in following: the value of half the hinge range is equal to 5912 = 29. and M e r analysis is therefore warranted. it may appear fiom the various diagrams that the situation is unacceptable and that the distribution is not at al1 normal. except for the lower end outliers. .5 mV. respectively.
.
O N P n N O P * N P N N N N I .
examination of the normal probability plot suggest that the majority of the variables are concentrated below 5000 ohmcms. but that there are a significant number of points which are several orders of magnitude larger. the situation is not the result of one or two extreme values. it appears that the whole set of observations contribute to the distorted shape of the boxplot and normal probability plot.5 displays the information produced by SAS for the variable Resdir. it appears that the entire set of values contributes to the problem. In fact. Furthermore. it is not only the extreme points that contribute to the distortion of the diagrams. There is a very large difference between these values and the actual quantiles reported in Table 4. but also the entire body of the values. These values are far fiom the calculated quantiles of 4800 and 1296 ohmcms. examination of the normal probability plot . Ressat Figure 4. Unlike the case of the redox potentials. respectively. Examination of the quantiles rtveals the following: half the hinge range is equal to 350412 = 1752 ohmcms and 2259 I 1752 = 401 1 and 507 ohmcms. This will be studied in the next section. As in the case of Resdir. it appears fiom the various diagrams that the situation is unacceptable and that the distribution is not at al1 normal. Once more. This can be concluded form the examination of the quantiles. including the stem and leaf diagram. the box plot and the normal distribution plot.Resdir Figure 4.6 displays the information produced by SAS for the variable Ressat. including the stem and leaf diagram. Furthermore. that is 8376 and 876 ohmcms. The Resdir values range between 173 and 22080 ohmcms. It appears that a logarithrnic transformation may be indicated. The Ressat values range between 73 and 183400 ohmcms.5 and therefore. The value of half the hinge range is equal to 925212 = 4626 ohmcms and the predicted quantiles are equal to 3750 + 4626 ohmcms. the box plot and the normal distribution plot.
26 d y r .seems to suggest. CorrRate Figure 4. that a logarithmic transformation may be able to correct the normality problem. Chloride Figure 4. Besides the outliers.26 d y r . respectively. This indicates a small deviation ftom normality. . as in the case of Resdir.e.7 displays the information produced by SAS for the variable Chloride. the data points seem to be well distributed and the box plot appears to have a standard shape. These values are far ftom the calculated quantile values of 481 and 58 ppm. There are two outlien: 0. Furthermore. The usefulness of a transformation will be studied in the next section.5 ppm. including the stem and leaf diagram.5 = 401. the box plot and the normal distribution plot.5 ppm and 21. as in the case of Resdir and Ressc!. the box plot and the normal distribution plot. Examination of the quantiles reveals the following: half the hinge range is equal to 42312 = 211.06 and 0. examination of the normal probability plot seems to suggest. Fially. the normal distribution plot is not exactly linear. and this is quite evident when the stem and leaf diagram and the box plot are studied. The Chloride values range between O and 22664 ppm. in fact it appears to be slightly curved. As in the case of Resdir and Ressar. The data are positively skewed. The CorrRate values range between 0. it appears that the whole set of observations contribute to the distorted shape of the boxplot and normal probability plot. that a logarithmic transformation may be able to correct the normality problem.5 ppm and 190 i 211. i. the mean is slightly larger than the median. This generally indicates the presence of outliers in the upper end of the distribution.19 and 0.8 displays the information produced by SAS for the variable CorrRote. including the stem and leaf diagram.
r. Fin .. 2 + .N W.* . L EEZZOGZzOk O P P U ) " P U ) O m m E E l l r n V A ~ t t ."r<P P N P yo=N  8 " m NU)W N N o m N N n U 0 3 m C o l 4 0 U4 1 C a] S c &Eu 9 0 .4 o o o m n OP.1NW::Z."NW _ m . d " P 1 N N m .P m m w m . DL O " 7 2.Z m P P P .
. . . I .. * . . a . .m N O " O i n N O n 3 3 * 3 3 ' DI 4 O m O n E O * X a m f 1 3. . ... * .. .. . . .? O O i n r n P ' m N N " I I N 3 w . .. * + I N I OOrnLD.. Y V C  IOZDS mou m s s a s O Y 1 0 " ? 0 O P in N 2ô2 E I V . . * .. . . . . . c C a Y1 c 3U o z u s ". ..
. .. . N N 4 . . d m .Y I 0 0 0 m. . ~ N L i W O ~ O O r < Y I ~ O P r < O i O O o 0 m m . ? .m m N N m c ..P " . O W W r n . . O 0 0 . .
.
However. ions in the case of pH. and the variable LChl will replace Chloride fiom this point fonvard. The shape of the boxplots is acceptable. The transformation of the remainimg variables: pHdir. The transformation proposed is the replacement of the original value with the logarithm of that value.2) is repeated using the logged data. fiom this point fonvard. Of al1 the transformations. are presented in Tables 4. These new variables.4. squarerooted. and the normal probability plot is very close to being perfectly linear. The analysis performed on the original data (Section 4. and 4. the distribution has greatly improved. and the results are presented in Figures 4. weight and concentrations. the distribution has also improved dramatically.11.2 Transformation of Variables There are rnany different ways to transform data. and rnay be rendered 'normal' by the log transformation. The transformation is therefore considered a success and.3.1. the one that may be of value is the logarithmic (or log) transformation. The variables which appear to be in most need of transformation: Chloride.9. Like Chloride. referred to as LChl. these variables represent the concentrations: and oxygen in the case of the redox potential. unlike Chloride. pHsat. In the case of LChl . each one seems to work best on a particular type of variable. Reddir. inversed.4. This transformation is considered a success. Although a transformation can be applied to any variable.1. The normal probability plots of these three variables are very similar. The variables being studied represent concentrations (as in the case of pH. and Redsat. and the normal probability plots are fairly linear. which is typically applied to variables representing physical characteristicssuch as length. the . 4. Resdir. LResdir and LRessat. and Ressat are studied first. redox potential and chlorides) and physical characteristics ( such as soi1 resistivity). and 4. In the case of LResdir and LRessat. the variables LResdir and LRessat will be used instead of Resdir and Ressat.2.10. and it is suspected that the same transformation can be useful for al1 three. The boxplot has a shape which is alrnost perfect. and so forth. The values can be logged.
For this reason. Redsat. The values of the new variable. which are already the result of a logarithmic transformation. For this reason.4. it is bener not to include them at all. In conclusion. but represent the concentration indirectly given that these concentrations have been logged. through a series of transformations. It is possible that a transformation will render the data more attractive. but it must be understood why a transformation is performed. . if these transformations cannot be justified or understood intuitively. LResdir. pHsut. n i e formulae for obtainiingthe pH and the redox potential. may be made to exhibit characteristics of 'normality'. LChl. denoted LCorr. of a solution are the following: It can be clearly seen that the pH and the potential4 are not direct measurements of the concentration. Reddir.12. the original variable will be retained for the analysis to follow.concentration hm already been logged in obtaining the pH and the redox potential. are presented in Table 4. 4. it is considered unreasonable to perfonn a second logarithmic transformation on these variables. the following discrete variables will be used 6om this point fonvard: pHdir. However. It c m be seen that the distribution of the data has not improved much. The LCorr values were analyzed and the results are presented in Figure 4. another variable which is considered a candidate for the log transformation is CorrRate. and CorrRate. Finally. LRessat. Any data.
255 0.748 2.322 1.342 2.525 2.513 2.732 1.880 2.364 3.173 2.816 2.O4 1 1.855 4.639 1.908 2.544 1.1 \ .556 2.190 2.474 3.072 2.204 2.855 2.813 3.651 3. (ppm) LChl 1.045 2.845 1.771 2.626 2.396 2.3 11 2.294 2.464 2.467 2.090 2.951 2.610 1.201 1.264 2.592 2.806 2.886 1.204 1.170 2.908 3.477 1.892 2.538 3.43 1  >le4.580 3.307 2.580 1.857 3.170 2.699 1.099 2.196 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 ues of LC LChl @Pm) Soi1 # 3.663 1.255 1.039 2.954 1.000 0.129 3.380 1.903 3.225 1.662 3.744 2.730 2.763 1.623 1.913 2.117 3.994 3.903 2.
.
S o i l#    1 2 3 4 5 6 7 8 9 1O 11 12 1 3 14 1 5 1 6 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 S o i l# 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 1 O0 101 102 1O 3 104 105 106 107 108 109 110 111 112 113 114 115 Il6 117 es of LR S o i l# Il8 Il9 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 247 Soil #     .
.
Table 4 3 Values of LResrol 122 .
w n m N n a . . ". . .m .N. N.. 4 w w .
4 Valua of LCorr  124 .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 26 27 28 29 30 31 32 33 34 35 36 37 38 39 Soil # 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 Soil # Soil # 79 80 81 82 83 84 $5 86 87 88 89 90 91 92 93 94 95 96 97 98 99 1O0 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 247 Soi #   Table 4.
.rnN"YIN in0 I O N 0 0 0 . : z . . . . . Y 3 3 3 0 0 ""3 I m w w P P m m m m 0 0 ~ 3 N I I I I I I I I 84433 l ... .. 8 .
n i e first step is to regresç each X variable individually and to observe the residual distribution. Figures 4.e.Fratio. Furîhermore. Outliers identified by a Cook's Distance (CD) >l. outliers on the model chosen to fit the data. Here. In this section. Stem and Leaf diagram. For each variable. the box plot. In a later section.Sa and 4. R2. the outliers on the residuals are examined.5b display the information related to the variables pHdir and a a pHsut. and the search for the missing X variable to be added to the model will continue. respectively. Outlien identified by a zscore > 3. y ).13a through 4. it will be assumed that model is not correct. a complete model (consisting of a cornbiiation of X variables) is regressed against CorrRate and a normal distribution is anticipated.1. and the normal probability plot for the residuals.13d display the SAS output for the variablespHdir and pHsot. If this does not occur. . i. In the previous section. It is most probable that the distribution will not be perfectly normal. PRESS statistic. This usually suggests that another X variable should be added to the model to account for the variance which was not accounted by the f i s t variable. and to keee track of the outliee on Y. it is tirne to study the distribution of the residuols arising fiom the regression of the independent variables with the dependent variable CorrRate. the goal is to study the distribution of the residuals for signs of anomalies.4. the outliers obtained were outliers on the X variable only. SSE. box plot and normal distributionplot constructed from the set of residuals. the stem and leaf diagram. includiig the e vs. pHdir and pHsat Tables 4.3 Remession of the Individual Variables Now that the distribution of each variables has been studied. y plot. predicted value of y ( e vs. the following information was extracted and examined: a a Number of observations N. R2adjusted. Plot of residuals vs.
SSE SSE The above percentage gives an idea of the ability of the equation to fit foreign data.e. ï h e increase in the error sum of squares was 8%. i.Residual Informatiou: VariablepHdir N SSE PRESS statistic 1 R ' R'adjusted FRatio Outlien with z > 3 Outliers with CD > 1 Table 45a Residual Characteristies:pHdir Residual Information: Variable pHs@ PRESS statistic z>3 Outliers ~4th Outliers \sithCD > 1 I l Table 4.5b Residual Characterktics: pHs01 Only 74 observations were available for regressing the variable pHdir against CorrRate. to fit data which were not a part of the observations used to create the equation itself. This value is obtained by the following equation: % increase in the error surn of squares = PRESS . which is quite acceptable. .
and that one point in particular (#72) is much higher than the nom. However. as such. indicates that some other variable should be added to the model ofpHdir alone. The Fratio is used to determine if the variable is significant in predicting y. and that the addition of another variables may be necessary. i.e. For every variable.00 (see Figure F. the observation is considered a residual. This can also be determined by studying the shape of the cuve of the normal distribution plot. This can also be seen on the boxplot where observation #72 is clearly an outlier. y plot is used to identifi any underlying trends in the distribution of the residuals. as suspected. normality of the residuals is determined using the e vs. that not al1 the variance in the system has been accounted by the model proposed. Fially.05 mmlyr. Finally. and therefore. When the zscore of a residual is larger than 3 andor when the value of CD is larger than 1. the e vs. The e vs. The outliers are identified by two different methods: by the zscore of the residual and by Cook's Distance (CD).Another way to measure this is to compare R2.00 and. to R2. pHsat is considered . which is substantially higher than the critical value of 4. as suspected. which is acceptable. the shrinkage is 9%. y plot does not show any clear trends in the distribution of the points. and the normal distribution plot. this generally indicates that the proposed model is not a complete one. if the plot shows a particular pattern in the residuals. in the case of pHsut. and on the normal probability plot where the outlier is located far above the c w e . any nonlinear c w e would indicates a deviation from normality which may be corrected by the addition of another variable. 74 observations were analyzed and revealed an Fratio of 4. observation #72 is considered an outlier with a zscore > 5. The decrease in R2is called the shrinkage.l) and. in the case of pHdir. This value is larger than the critical value of 4.61.12. ï h e value obtained for pHdi is equal to 10. y plot. Furthemore. observation #149 has a zscore close to 3 and should also be examined in future analyses. the cuve on the normal probability plot is slightly c w e d which. A straight line is characteristic of a normally distnbuted set of values. it does show that the majority of the residual values are between i 0. in this case. pHdir is considered significant in predicting CorrRate. and it represents the decrease in predictive power of the equation when used on the population as a whole.
and a 24% decrease in R ~ . Furthermore. . However. because one variable is k i n g studied at a tirne. This will be discussed in a later section. there is an 8% increase in the error sum of squares. it cannot be concluded that pHsat will not be better in predicting CorrRate when it is used in combination with other variables. From the above results.to be significant in predicting CorrRate. it is clear thatpHsat is not as good aspHdir in predicting CorrRate. even though the distribution of the residuals is very similar.
m w m P m .C .r m n o 193 0 0 0 I O S O Z s s s s s OYIOYIO O P Y I N X U C 4 n *LI*  :ô20 .N T m m o r .e m n o .0 "LI . O . ? ?Y&? 0 0 1 Y) P O 3 W N P m .0 0 E l u .
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including the e vs. y plot.6b display the information related to the variables Reddir and Redsat.6a Residual Cbaracteristics: Reddir Residual Information: Variable Rea3at I N SSE PRESS statistic R~ R~adjusted FRatio i t hz >3 Outliers w Outliers w i t h CD > 1 Table 4. R Residual Information: Variable Re& N SSE PRESS statistic R2 R2adjusted FRatio i t hz >3 Outliers w Outliers with CD > 1 . Figures 4. the stem and leaf diagram.14d display the SAS output for the variables Reddir and Redsot. Furthemore. the box plot. respectively.Reddir and Redsat Tables 4.14a through 4. and the normal probability plot for the residuals.6b Residual Cbaracteristics: Redsal . Table 4.6a and 4.
the normal probability plot indicates a deviation fiom normality. which is far below the critical ratio of 4. n i e results obtained fiom Reddir appear to indicate that this variable will not play an important role in future analyses. The e vs.05 mm/y. the results indicate that this variable performs worse than Reddir. and the extremely low value of R2 indicates that there is little correlation between Redsat and CorrRate.Only 74 observations were available for regressing the variable Reddir against CorrRate. the only bue outlier is observation #72. This is also indicated by the value of 0. y plot shows that the majority of the residuals are between k0. In the case of Redsat. which shows that the correlation between Reddir and CorrRate is very low. There are two points which appear to be located far fiom the rest: observation #72 and #149.00 and which indicates that Reddir is not significant in predicting CorrRate.0012 clearly shows that this variable is not significant in predicting CorrRate. . The Fratio is equal to 0. This will be s h o w to be true in the following sections.324. as well as the presence of the two outliers which are located far fiom the line. The Fratio of 0. but #149 should also be observed because of its hi& zscore. According to the zscore and Cook's Distance. Fially.0044 for R*.
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including the e vs. Figures 4.7a and 4.15a through 4. and the normal probability plot for the residuals. the stem and leaf diagram.7b Residual Characteristics: LRessal .7a Residual Characteristics: LResdir Residoal information: Variable LRersnf N SSE PRESS statistic R2 R2adjusted FRatio Outliers with z > 3 Outliers with CD > 1 Table 4.15d display the SAS output for the variables LResdir and LRessat. y plot. Residoal Information: Variable LResdir N SSE PRESS statistic R2 R~adjusted FRatio Outliers with z > 3 Outliers with CD > 1 1 1 I Table 4. the box plot.7b display the information related to the variables LResdir and LRessat. Furthemore.LResdir and LRessai Tables 4. respectively.
the results suggest that LRessat is better that LResdir in predicting CorrRate. 70 observations were used. with observation #149 also has a high zscore. ïhis is contrary to the expectation. These two residuals also appear on the normal probability plot as points located off the curve. as such. Once more.in the case of LResdir. Furthermore. 74 observations were analyzed.06 d y r . in general. as seen in Figure 4.00 and indicates that the variables is not significant in predicting CorrRate. observation #72 is identified as an outlier. Furthermore. when applying the equation to the population as a whole.598 is also below the cntical value and therefore.553. The e vs. y plot shows that 95% of the residuals are between 10. the analysis shows that LRessat is not significant in predicting CorrRate. The curve of the normal probability plot also suggested a slight deviation form normality.04 d y r . . These values are somewhat higher that expected. considering the importance of resistivity in the corrosion process. contrary to what is expected. observation #72 is identified as an outlier. There is a 39% decrease in the R2value and a 14% increase in the error sum of squares.with only two residuals being above 0. The Fratio obtained is 2. there is a 39% decrease in the R2 value and a 4% increase in the error sum of squares. with observations #149 and #42 exhibiting nutlier behavior. The e vs.16d. with only two residuals above 0. The Fratio of 2. y plot shows that 90% of the residuals are between 10. which is below the cntical Fratio of 4.06 mdyr. in the case of LRessat. This is the expected result because CorrRate was obtained by testing a soi1 which has been saturated with distilled water and. whose resistivity during testing was better represented by Ressat than by Resdir.04 d y r .
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Fially. y plot. the normal distribution plot shows a slight deviation fiom normality which may be corrected by the addition of another variable to the model. the stem and leaf diagram. includiig the e vs. 73 observations were used to analyze the relationship between LChl and CorrRate. y plot.16b display the SAS output.00 and.572 is much higher than the critical value of 4. as such. Figures 4. The decrease in R~is only 12% and the increase in the error sum of squares is 7%.8 displays the information related to the variable LChl. . The Fratio of 8.04 M y r . the box plot.06 M y r . Furthermore. Furthermore. Residual informatiou: Variable LChl N SSE PRESS statistic R~ R~adjusted FRatio Outliers with z > 3 Outliers with CD > 1 Table 4. with only e two outliers above 0.LChl Tables 4.8 Residual Characteristics: LChl In total. where 95% of the ' residuals are between rt0. with #42 exhibiting outlier behavior.16a and 4. These value are quite acceptable. This can also be seen on the e vs. and the normal probability plot for the residuals. observations #72 and #149 are identified as outliers. this variable is considered very significant in predicting CorrRafe.
.
.
they inhibit the formation of the protective passive layer on the steel specimen. It was thought that because resistivity indirectly measures the chloride content. On the other hand. . 4. the insignificant role of Reddir comes as a surprise.4 Correlation Matrix In the previous section. The influence of the chloride content was also expected. The correlation matrix for the data under study is presented in Figure 4. the relationship between CorrRate and each of the independent variables was studied. The variables which appear to add the least information are Reddir and Redsar.The results analyzed up to this point suggest that the pHdir variable performs the best. However. plus the dependent one.17.pHsut and LRessar. they decrease the resistivity of the soi1 because they are ions and conductive by nature. as such. as well as the general ionic content of the soil. and secondly.1. It is not at al1 surprising that the pH valuc plays such an important role. Firstly. An alternative to this is to study the correlation matiix of the set of independent vanables. that LRessar would provide almost as much information as LChl . followed by LChl . Chlorides have a dual effect on the corrosion rate. One could easily proceed and regress each variable in turn with al1 the others in order to identifi the extent to which the variables are intercomlated. what is very surprising is the insignificant role played by the variable LRessat. this has not been s h o w yet. The other reaction expected is the reduction of 0 2 and. as the reduction of H' ions is one of the iwo reactions expected to contribute to the corrosion problem.
.
the lower the corrosion rate.pHsot and LRessar. However. An examination of the correlation between CorrRaie and the independent variables will quickly reveal that the results are the same as those obtained in the previous section: the pHdir variable perfonns the best. Reddir and Redsaf. One would expect that the corelation would be negative. The results obtained are therefore misleading. LRessot and LResdir. This indicates that the information provided by the variables is essentially the same. it remains to be determined whether or not the extra information provided by LChl is sufficient to consider this variable significant when the variable LResllir is already known. As each of these pairs essentially measure the same soi1 property.e. it must be kept in mind that the variable LResdir was obtained by testing the soi1 in the state in which it was received in the laboratory. and this indicates that the two variables essentially provide the same information. and that only one of the two variables needs to be included in a model. Another correlation of particular interest is that between LChl and each of the resistivity variables. The correlation between LChl and LRessaf is very high. it is not at al1 surprising to see high correlations. which means that some soils were tested when dry and others were tested in a saturated condition. Another important fact observed fiom the correiation matrix is the presence of high correlations betweenpHdir and pHsa!. redundant information. i.The ideal situation is one in which the correlations between the dependent variable (CorrRare) and each independent variable are high. This would result in the least amount of multicollinearity. i. and would lead to a situation where each variable that is added to an equation would provide new information and would serve to significantly increase the effectiveness of the equation. The choice of the variable to be retained will be discussed later. Although LChl is the better of the two variables. Another important point is the sign of the correlation between CorrRafe and LResdir. The variables which appear to add the least information are Reddir and Redsar. and between LResdir and LRessaf. but this is not the case.e. followed by LChl . This is the first step in the determination of a model which describes the corrosion . The correlation matrix provides information about the interaction of the variables. the higher the resistivity. and the correlation behveen the independent variables themselves is low.
As expected. Furthermore. it can be safely concluded thatpHdir outperformspHsat. the models containing pHdir almost always perform better than those containing pHsat. LRessat never does. This was an expected result. This procedure is considered better than the stepwise. which suggests that the information provided by each of the variables is not necessarily repetitive. The next step consists of comparing the possible models. and that LResdir appears in almost al1 the best 2 and 3variable models. Furthermore. which will be done using the RSQUARE procedure in SAS.9 presents several 1. And finally. fonvard. Table 4. 3 and 4variable model which are made up of a combination of variables which is considered acceptable by the analyst. 3variable models. 2. when LRessat appears in r few. even though LResdir often appears together with LChl. the variables which appear to be correlated best with CorrRate are the pH variables. For this reason.1. 4. in the case of the onevariable model. the results obtained are similar to those obtained in the previous exercises. instead.5 RSOUARE Results The RSQUARE procedure in SAS is used to obtain a list of the 10 best 1variable. it provides the analyst with a set of models that perform best. it is swprising that the variable LResdir performs better than LRessat. Another important result is that pHsot andpHdir never appear in the same model. these two variables often appear in the same models. This suggests that the information provided by one variable is not necessary when the other variable is already in the model. and backward regression procedures because it does not present one final model as the best model. 2variable. These results will be considered M e r in a later section. etc. However. and allows the analyst to compare the models and to select the one shown to be the most logical.phenomenon well. . and LChl .
This is certainly a surprishg result that will be considered further in a later section. Variables in Mode1 PHDIR PHSAT LCHL LRESDIR LRESSAT REDDIR REDSAT LRESDIR LCHL PHDIR LCHL PHDIR LRESDIR PHSAT LCHL PHDIR LRESSAT PHDR REDSAT PHDIR REDDIR PHSAT LRESDIR PHDIR LRESDIR LCHL PHSAT LRESDIR LCHL PHSAT LRESSAT LRESDIR REDSATLRESDIR LCHL REDDIR LRESDIR LCHL REDSATLRESSAT LRESDIR REDDIR LRESSAT LRESDIR PHDIR REDDIR LRESSAT LRESDIR PHDIR REDDIR LRESDIR LCHL PHSAT REDDIR LRESDIR LCHL Possible 1. although Resdir does. Redrat does not appear in any of the models and.3.Finally. and 4 Variable Models  . it does not appear to play a very important role.2.
Furthermore. for each of these three categories. to examine the effect of the variable Soiltype. pHdir performs best. 5 ) .18a through 4. the variables which perform best arepHdir and LChl . the variables which perform best are LChl and LRessat. the pH of a soi1 seems to be more important when the soi1 is a clay. Then. and clay. Conversely. This exercise consists simply of calculating the correlation matrix and performing the RSQUARE procedure on the data which has been sorted. a simpler exercise will be performed to investigate the general effect of the categorical variables. The above results suggest that the variable Soilfype plays an important role. following important points are extracted form the matrices: a The correlation matrices obtained for the variable Soiltype are presented in Figures 4. For example. only discrete variables have been considered. LRessat performs very poorly. The redox variables appear not to be very helpful. sandlclay.4. One way of includiig categoncal variable in the analysis is to transform each one into a set of . the data is first sorted into the three categories: sand.18~. For sands. .1. and as such. It is therefore concluded that the variable Soiltype should be included in future analyses. The For clays. this categoncal variable will be transformed into a set of three dummy variables and treated in the same manner as the other discrete variables. The pHdir variables seems to perform poorly. the variable Reddir performs quite well.The dummy variables which can then be treated like discrete variables (see Section D results of such an analysis are not very obvious. and for this reason. and the chloride content appears to be important irrespective of the soil type. The influence on the categoncal variables such as Soiltype. For example. Furthermore. the correlation matrix is calculated and the RSQUARE procedure is performed. followed by LChl aid LRessaf which perform equally well.6 Cateeorical Variables Up to this point. For sandclays. and the resistivity is more important when the soi1 is a sand. Moisfure and Sulflhave been ignored. both variables are important when the soil is a sandclay.

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PHDIR PHDIR 1.00000 0.0 54
PHSAT 0.61974 0.0001 51
REDOIR 0.03843 0.7826 54
REOSAT 0.03715 0.7897 54
LRESDIR 0.06464 0.6660 47
LRESSAT 0.13583 0.3419 51
LCHL 0.01416 0.9223 50
PHSAT
REDDIR
0.03843 0.7826 54 0.03715 0.7897 54 0.06464 0.6660 47 0.13583 0.3419 51 0.01416 0.9223 50
0.06473 0.6452 53 0.23635 0.0884 53 0.02610 0.8633 46 0.26105 0.0671 50 0.20294 0.1620 49
1.00000 0.0 54 0.82414 0.0001 54 0.38833 0.0070 47 0.37746 0.0063 51 0.41076 0.0030 50
0.82414 0.0001 54 1.00000 0.0 54 0.22604 0.1266 47 0.40600 0.0031 51 0.48817 0.0003 50
0.38833 0.0070 47 0.22604 0.1266 47 1.00000 0.0 47 0.74594 0.0001 47 0.57108 0,0001 45
0.37746 0.0063 51 0.40600 0.0031 51 0.74594 0.0001 47 1.00000 0.0 51 0.88587 0.0001 48
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Figure 4.18b SAS Outpuk Correlation Mntrix for Sand Snmplcs




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The results obtained fioz?. the RSQUARE procedure indicate that the variables
LChl and pHdir play a very important role, and that both the resistivity variables
conhibute new information.
In some cases, LRessat performs bener than LResdir, and
in other the opposite is tme. Furîhermore, the variables LChl and LResdir often appear in the same model, whereas LRessot rarely appears in a model wi?hLChl . It is becoming clear that the variables LRessat and LChl provide overlapping information, and that
LResdir appears to represent some other inherent characteristic of the soil.
AAer a similar analysis involving the categoncal variables Moisture and Sulf7, it was concluded that these variables do not introduce new information, nd it was decided that they will not be considered in future analyses. In the case of the variable Moisture, it is not at al1 surprising that the variable is unnecessary. Moisture is a measure of the saturation state of the soil as it was received in the laboratory. This is not the state in which the soil was tested to obtain the value of CorrRote, the dependent variable. Therefore, the variable Moisture cannot be usehl in predicting the value of CorrRate when it is so wholly unrelated to the conditions under which CorrRote was obtained. The variable Sulji appeared to provide no new information, and was considered not io be useful. However, it is believed that this conclusion is not one that would necessarily apply to future studies. The sulfide content of a soil is generally considered an important influence on corrosivity. in fact, sulfides (s*) are very corrosive and can cause severe damage to metal surface. The fact that the variable SuIf7 does not play an important role in this analysis may be a result of errors in the testing procedure. Another reason why the effect of sulfides is minimized may be due to the fact that sulfides are only measured quantitatively. Perhaps sulfide content should be measured with more This sirnply means that it may be precision, as in the case of chlonde content.
insuficient to qualiQ a soi1 as containing either no sulfides (N), trace amounts of sulfide
(T), or a lot of sulfides (P). in the case of chlonde content, it was observed in Section
4.1.2 that the variable characteristics, pnor to the logarithmic transformation, were simply unacceptable. The variable Chloride did not exhibit normality, and could not be used in regression analyses. Like the chloride content, sulfide content is a concentration, and it
it was decided to include both variables in future analyses. and only a small amount of water is added prior to testing for CorrRate. Which one of the two represents most accurately the conditions under which the variable CorrRate was obtained? PHdir was obtained by testing the soil as it was received in the laboratory. Although LRessat is the variable which represents the condition of CorrRate testing most accurately. Many different variables were measured during the experimental portion of this project. the variable Reddir is considered the most representative variable of the two. Redsat. 4. For this reason. but the reason they were measured should be remembered. However. whereas pHsat was measured when the soil was supersaturated. However. only the variables which are considered useful in predicting the dependent variable CorrRofe will be retained. al1 of the discrete variables were included in the analyses. pHdir is considered to be the most representative variable of the two. the soil is greatly beyond saturation.7 Variables Retained For Further Analvses Up to this point. This will be discussed further in a later section. When the soil is mixed with water at a ratio of 1:1. This step is one of "cleaningup". in the case of LResdir and LRessat. Not al1 of the variables can provide information on the phenomenon measured by the variable CorrRate. in the case of Reddir vs. the soil tested for CorrRafe is just barely saturated. the soil received in the laboratory is already moist. the variable LResdir appears to introduce information . it is felt that Redsaf is not a good measure of the oxidationreduction potential of the soi1 because of the large quantity of water added to the soil pior to testing. in most cases.1. it has become clear that some variables perform better than others. From this point on. It is felt that the method used to obtainpHsat is unacceptable. The water added contains a certain amount of oxygen which will influence the readiig. For this reason. The first step is to choose between the pH variables.may be necessary to perform a similar transformation on this variable before it can be used.
and Soiltype. 4. This suspicion arises fiom the fact that the majority of the soils obtained in the laboratory are already moist. It is further suspected that the property represented by LResdir may be the soil type. However. LResdir. LChl .that LRessat does not. or the soil content.a.1 Determinine Sienificance Now that the general behavior of each variables is understood. The goal of the analysis is to answer the following hvo . they have a very similar moisture content. In summary. Perhaps certain soil particles are inherently more conductive than others and that LResdir measures this phenomenon.pHdir. they do not have a moisture content which optimizes their conductive properîies until they are saturated. The variables on which attention is focused are the following: pHdir. Determinimg significance consists of studying the results of a series of ANOVA tables and detemining. An ANOVA table pemits rapid calculation of the Fratio and the correlation coefficient. until the movement of ions is optimized. Reddir. R~(see Section D. LRessat. such that its addition to a set of other variables increases the ability of the set to explain the phenomenon under consideration. at each step. whether the variable added is significant. LChI.2 Consideration of Chlorides in Predicting the Corrosion Rate 4. It may be possible that LResdir measures some conductiveproperty of the soil which is not the result of the movement of the ions in the soil. Le. A variable is considered significant if the information provided by this variable is sufficiently important. LRessat. i. It is suspected that LResdir represents some inherent property of the soil which inîiuences its resistivity. the following variables are retained for further analyses: CorrRare. It is for this reason that both LRessat and LResdir are retained for further analyses. LResdir and Soilrype. it is time to determine the significance of the chosen variables.4). The term signiycance refers to the statistical significance of a variable.2.
of each of the two models. and 'Does the variable LResdir provide the same information as Soiltype and. The following information is entered in the ANOVA table. and The cntical Fratio with which the calculated Fratio is compared. and is required to determine significance of a model R: a A benchmark model. SSE. For the sake of simplicity. a. l . should it be included in a model containing the variable Soiliype?'. a The error sum of squares. a The degrees of fieedom.questions: '1s the variable LChl necessary when LRessat is already included in the model?'.to which rnodel R is compared. the cntical Fratio will Variable in Mode1 Intercept Intercept + Soiltype Intercept + pHdir Intercept + LChl Intercept + Soilîype + pHdir Intercept + Soiltype + LChl Intercept + Soiltype + LRessat Intercept + Soiltype + Reddir Intercept + Soiltype + LResdir Intercept + pHdir + LResdii Intercept + Soilspe + pHdu + LChl Intercept + Soiltype + pHdu + LRcssat Intercept + Soiltype + pHdir + L R e d i Intercept + Soiltype + pHdir + Reddu Intercept + Soilspe + pHdi + LChl + Lressat DOF SSE Table 4. The critical a Fratio is obtained from Tables D . if so.10. of each of the two models. DOF. The SSE and the DOF of the possible models are listed in Table 4.10 Possible Modelr with Corrnponding SSE and DOF Values 161 .
and 3.70 R~ 0. The next step consists of determinimg which variables can be added to Soiltype and pHdir significantly. but only the tables considered relevant are presented here.06185 MS F 0.and the results indicate that only pHdir. This variable is selected first because of the need to determine if the variable LResdir represents some aspect of Soiltype. This is a conservative choice. The fdlowing ANOVA table results: SOURCE Difference .12 The resuits indicate that the variable Soiltype is indeed significant. The next step is to determine which variables cm be added to Soiltype significantly.15 when comparing two models with a difference of 2 DOF's. As suspected.00079 4.00 when we are comparing two models with a difference of 1 DOF.interce*+ Soilwe(S2) intercept(o) DOF 2 68 70 SSE 0.be taken as 4. There are an infmite number of ANOVA tables which can be constructed &om these variables. n i e model tested (R) and the model against which it was tested (o) are presented along with the Fratio and the result of the significancetest. Each variable is tested in tm. Each of the remaining variables was tested in tum. whether it is significant or not.O5 and a DOF of 60 for the Rmodel. and the results indicate that both LChl and LRessat can be added. with variable pHdiï pirforming best. LChl and LRessat can be added.05433 0. The following ANOVA table results: . LResdir cannot be added to pHdir and Soihype with significance. i.e. These values correspond to an a value of . The first step of the analysis is to determine if the variable Soiltype is significant. It would be interesting to see whether or not LResdir could have been added topHdir if Soiltype were not already in the model.00376 0.00752 0.
As stated earlier. conductivity of certain types of soil particles. The corresponding ANOVA table. The question that m u t now be answered is whether or not LChl is necessary when LRessai is already in the model.00000 0. or even the air content. in this state.04032 0.The results indicate that LResdir could have been added to pHdir if Soiliype were not already in the model.00000 0. Perhaps LResdir measures some property of the soi1 independent of conductivity related to the ion content. the model. resistivity measures the conductivity of a soi1 due to particle charge. and vice versa. both LRessat and LChl can be aaded to pHdir and Soilfype sigiificantly.00 0. It appears that these two variables contribute similar information. LResdir was determined by testing a soil which was not saturated with water. It may be possible that. witn LChl performing better than LRessat. as such.00 . one variable is unnecessaty when the other is present in Difference intercept + Soiltype + pHdir + LChl + LRessat R intercept + Soiltype + pHdir + LChl (o) l 0. but was only moist.00062 0.04032 0. in which the model pHdir+Soiltype+LChl +LRessat is compared to the model pHdir+Soiliype+LChl follows: Perhaps these soil properties are taken into account by the variable Soiltype and.
is strongly believed that the effect of chloride ions is very important and that. the other is not needed. It was one of the objectives of this thesis to detennine whether or not the determination of chloride concentration is essential to estimate the corrosivity of a soil. 1s the addition of LChl to a model containimg Lressat necessary? The following ANOVA table illustrates the situation: The results indicate that LChl need not be added to the model when LRessat is already included. but the effect of chloride ions is so important that m e r research is warranted. even though the presenr results show that chloride ion concentration need not be added to the existing grids. but it is also a variable which is much more difhult to obtain. i. The better variable is LChl . the model which appears to provide the most information with the least amount of redundancy is the following: Soiltype + pHdir + LRessar. It was initially suspected that the concentration of conductive chloride ions was already incorporated in the resistivity measurement. when one of the two variables is included in the model. in conclusion. In fact. it is suggested that the variable LChl need not be added to the existing . Although either one of the two variables can be added to the pHdir+Soiltype model. obtainiig the chloride concentration is more time and effort consuming. If so.It is very clear that the variable LRessar need not be added lo the model containhg LChl . the measurement of chloride concentration provides invaluable information to the potential corrosion problem. PACE and AWWA. a suggestion would be made to incorporate the chloride ion concentration into the existing grids to estimate corrosivity. As it was described in Chapter 2. For the moment.e.
For this reason. in a data set made up of 150 observations. one includiig the outliers and the other excludiig them. for the sake of completeness. in general. The information provided by this parameter can be invaluable in certain cases. Certain differences did appear and they warrant some attention. However. This does not mean that they must be eliminated from the set.corrosivity grids. The results are then compared and the f i a l conclusions are drawn. in fact. A popular way of dealing with outliers is to perform two separate studies.2 The Effect of Removintr Outliers Outliers can have a very large influence on the results obtained using regression analysis. in this case. the outliers have been identified as observations # 72 and # 149. 4. These observations have unusually high corrosion rates which the variables studied were unable to explain fully. the variable LRessat performs more poorly and. and is not included in the fia1 model. If a soi1 testing laboratory is equipped to test for the chloride ion content. It is incorrect to simply eliminate an outlier from a data set simply because its behavior is different from the rest of the data. the analysis was repeated on the data set without the two outliers. as a consequence. a a The variable LChl appears to be even more important than before. On the contrary. these two soils should be studied further because they may provide information unlike al1 the other soils.2. However. it must be remembered that the variable LChl performed bener than the variable LRessat and that the only reason that the suggestion of replacing LRessar with LChl was not made was because the chloride content is more difficult and time consuming to obtain. . These difference are: a The variable Soiltype does not appear to be very significant. the presence of one or two deviant observations is not unusual. then it is recommended that they do so. The conclusions drawn from the results obtained are very similar to those obtained from the complete data set. outliers must be identified and studied carefully.
Any legitimate corrosion testing Company is already aware of the importance of chloride ions in the corrosion process. These results are difficult to accept. The results obtained up to this point do not suggest this conclusively. are responsible for the corrosive nature of the soils. can the two deviant observations be eliminated without M e r study? It is felt that. The goal of this report was not to convince the industry to begin testing for chloride content. Then why is this parameter badly represented in this data set? Furthermore. 4. it is important to determine the power of the statistical test.70 is generally considered acceptable. LRessar and the two soil type variables. the outlien should not be ignored. in this case. the analyst rnay choose to disregard the results obtained. Finally. The power will therefore be checked to ensure that the probability of finding the variable significant is adequate. How can the variable LRessat be useless? It is well known that the resistivity of a soil is a key indicator to its corrosivity. the variable LChl proved not to be significant when the variable LRessat was already in the model. A power of . When the variable LChl was added to the model consisting of pHdir. The goal of this report was to determine whether or not the suggestion should be put fonvard to add this parameters to the existing grids. the value of the power parameters were as follows: .The conclusion that would have been drawn fiom the above data set would be that the variable LRessar is not usefu! in determining corrosivity. it has already been determined that the variable LChl performs better than LRessar. which have not been studied up to this point. and is most probably already testing for this parameter. in cases when a variable is not significant. A low power may be the reason why a variable did not prove to be significant. in this preliminary analysis.3 Power Analysis The power of a statistical test is the probability of finding a variable significant when it is in fact so. It is also suggested that these two soils be studied M e r to determine what variable(s). and consequently. and that only LChl and pHdir can predict the corrosivity of a soil.
13).87.8.6 (see Equation D.K1=4 ks= 1 K= 5 The value of N. if it is so. . ïhis result indicates that the power of the statistical tests is not responsible for fmding LChl insignificant when LRessat is already in the model. The power of this statistical test is 0. is taken conservatively as 70 and the value of L is determined to be 9. which means that there is an 87% chance of h d i n g LChl significant. The power is obtained by interpolating between values obtained fiom Table D. the number of observations.
resistivity. soil type. certain limitations of linear polarization testing must be remembered. 153 soils were tested for the following: pH. The future migration of chlofide ions from the surface to the depth of the embedded metal.1 Summary of Results Each soi1 was tested accordiig to the AWWA Cl05 and PACE 823 Standards. For example. moisture content. or the presence of any extemal influences affecting the corrosion rate. the following possibilities cannot be accounted for: The presence of stray current corrosion. In sum. an accelerated electrochemical test used to evaluate the corrosion rate of ductile iron embedded in soil. 5.CHAPTER 5: CONCLUSIONS AND RECOMMENDATIONS In total. oxidationreduction potential. 0 Galvanic attack of a ductile iron pipe when connected to copper service laterals. However. the chloride ion content and the corrosion rate were obtained using the linear polarization test. and chloride ion content. drainage ability. and as such.2 for more details on possible future work). This data was analyzed using the Statistical Analysis System (SAS) and the following results were obtained: . and the applications in this field appear endless (see Section 5. Any future changes to the soil. this parameter must be considered one part of a complete study in the determination of the corrosion potential. The corrosion rate obtained using this method is the corrosion rate of the soil as it is found during testing. and additionally. cannot be accounted for by the method of linear polarization. sulfide content. Of these. and The potential establishment and proliferation of sulfatereducing bacteria. only the corrosivity ofthe soi1 itself is measured. 75 soils were tested uçing the method of linear polarization. ïhis testing method proved to be a powefil tool in the evaluation of soi1 corrosivity.
the method in which the soil is tested in its unaltered state proved to be the bener predictor of the corrosion rate. chlonde ion testing is t h e consuming and requires an experienced technician. of the two pH testing procedures. Although not included in the industry standards. when one variable is included in a predictor model. whereas chlonde ion content can only be measured under laboratory conditions. saturated. the resistivity measured when the soi1 was saturated with distilled water represented the bener of the two in predicting the corrosion rate. Although chloride ion content outperfomed soil resistivity. because this variable is currently being used in the industry standards. and as such. a a a Soil resistivity proved to be a good predictor of the corrosion rate. although not as good as expected. Soil resistivity was retained instead of the chlonde ion content. Furthemore. . and appeared in al1 the best predictor models. this variable was highly correlated with the corrosion rate. soil resistivity can be measured insitu. Furthemore. the power of the significance test was examined and was shown to be acceptable.The variable which plays the most important role in the prediction of the corrosion rate is the pH of the soil. it is suggested that chloride ion content not replace resistivity in the existing standards. saturated vs. The important role of chloride ion content in the predictions of the corrosion rate bas been established. the other variable is insignificant. the information provided by this variable will provide a bener understanding of the soil and its corrosive properties. unaltered vs. a The chloride ion content proved to be an excellent predictor of the corrosion rate. the additional information provided by this variable was not significant enough to suggest that it be added to a model containimg soil resistivity. Of the two testing procedures. and it can be determined rapidly and easily. The information provided by the chlonde ion content and the resistivity of the soil when saturated overlapped. Second only to pH. Furthemore. Conversely. It is therefore strongly recommended that this variable be tested whenever possible. unaltered. For these reasons of practicality.
This is a very surpriskg result. proved to be an insignificant predictor of the corrosion rate when the soil s p e was included in the predictor model. 0 0 The accuracy of the method of linear polarization can be studied further. Soil samples obtained from sites of pipe failures can be tested using this method. and clay content.The variable representing the resistivity of the unaltered soil. which is not possible in a set of randomly selected soi1 samples. measured as received in the laboratory. It appears that when the resistivity of a moist soil is measured. Soil samples should have a predetermined pH. the time the soil is exposed to air before testing. resistivity. and the addition of distilled water. that of sand particles. sulfide content. and as a consequence. This will enable the researcher to study the effect of varying one parameter at a time. i. a new set of soil samples should be created in the laboratory. chloride content. the Lherent conductivity of clay particles vs.2 Recommendations for Future Wnrk First and foremost.e. al1 served to alter the potential of the soil. The variable which proved to be the least important in the prediction of the corrosion rate is the oxidationreductionpotential of the soil. the conclusions drawn were essentiallythe same. and the results can be compared to the actual record of 'lears to break" or "breaks per year". All statistical analysis steps were performed on two data sets: one containing al1 observations. the result may indirectly represent some inherent resistivity which depends on the soil type. and another from which outliers were excluded. This requires a well organized. long term study in which a minimum of 100 soi1 . oxidationreduction potential. e. It is strongly suspected that the method by which the soil is handled.g. Although the numerical results varied. given the importance of this parameter in the corrosion process. 5. only a small correlation between the oxidationreduction potential and the corrosion rate was observed.
a thorough knowledge of the other influencing phenomena will enable the researcher to identify cases of stray current corrosion. Iinear polarization testing. It is also strongly suggested that the sulfide ion content be determined more accurately in future laboratory experiments. and which is the least subject to human error. as opposed to using a more representative specimen. and titration). and sulfide attack. and which are not measurable using the method of linear polarization. a Based on the method of linear polarization. . in the testing procedure outlined in this report. Soils are tested for pH. and that the results obtained using the tests described in this report may not be suficient to represent the true effect of sulfide ions in the corrosion process. Determine which method is most accurate. which is least subjective. oxidationreduction potential and resistivity immediately after. which may cause the pipe to fail prematurely. The effect of retaining only the fmest particles. a a Study the various methods currently being used to determine the chloride ion content (e. Furthermore. reading potentials. develop an insitu test for corrosion rate. This project is a very important one because it will create a proper base for further research in the area of chloride content. a Repeat the study undertaken in this report with the following changes: a Sulfide test is replaced by the actual sulfide ion concentration.samples must be analyzed and the background information related to the cortoded pipe m u t be gathered. Furthermore. only the finest particles of soi1 were retained for the chloride ion test. in order to ensure that al1 test are performed under the same conditions. Inconsistencies in the results obtained fiom the two tests suggest that the tests may be improved for future use of the AWWA and PACE standards.g. should be studied further. The tests used to determine the sulfide content should be investigated further. or before. galvanic attack.
laboratoiy testing can be done to determine the effect of temperature and moisture content on the corrosion rate. a Timedependent phenomena such as the development and subsequent proliferation of a sulfatereducing bacteria colony. e.Use the chlonde ion test which yields the most reproducible results. and Include the various types of metals in the study. and which is subject to the least human error. Using the method of linear polarization. study the variation of the corrosion rate NI rime. Consider incorporating temperature and moisture content in the existing grids to account for seasonal variations in these factors. Upgrade the soi1 type classification to include more types of soils. organic.g. can be studied by creating the proper environment. and silt. . Using the method of linear polarization. and the knowledge of insitu conditions will enable the engineer to determine the potential nsk for corrosion with more accuracy. and testing for the corrosion rate at given intervals.
. H. Y. and Pickering..G. 1989. 59611. W.. 30111. Academy of Sciences of the Ukraine. and Revie. National Association of Corrosion Engineers. September 1992. No. 5... paper no. V.H.W. 1969. Fontana. H. p. p.M. "Statistical Predictions of Corrosion Failures". M. No. "Determination of the Corrosion Activity of Soi1 in Relation to Steel by the Polarization Resistance Method".. 48. W.. McCawHill. p.F. Y. "Corrosion by Soils". J. and Young.. Andrade. p.BIBLIOGRAPHY Parker. and Feliu.C. Sehgal. V. 61.. New York. Materials and Structures. Corrosion. 47. Texas.. 108. Proceedings of NACE Conference CORROSION89 (New Orleans). "Polarization Resistance Measurements in Large Concrete Specimens: Mathematical Solution for a Unidirectional Current Distribution".A. Funahashi. May 1991. . R.. NACE Basic Corrosion Course. 1994. National Association of Corrosion Engineen. Corrosion. No. Proceedings of NACE Conference CORROSION94.. Kiev.. 596. p. 22. V. and ElTantawy. Houston. Institute of Problems of Material Science. and Greene. Gonzalez.D. UrquidiMacdonald. Vol. 1967.T. R. A. Texas. a7d Shvets. 706. paper no. Houston..3. 1989... RochaFilho.E. OsseoAszre. MayJune 1992. Feliu.. Corrosion and Corrosion Conbol... Vol. Vol. Macdonald. Lavrenko.D. S.T. C.. Rogers. p.A. p.A.W. Corrosion Engineering. B. Houston. M. 199. New York. Kho. Texas. N.. Translated fiom FizikoKhimichesknyaMekhanika Materialov. M. "Reproducibility of Polarization Resistance Measurements in SteelinConcrete Systems". Uhlig. 9. K.D. John Wiley Sons. D. National Association of Corrosion Engineers. 1985. 301. "Investigation of ELOG I Tests and Cathodically Polarized Steel in Concrete". 330. "Determination of the Polarization Resistance of Rebar in Reinforced Concrete".
[22] ASTM. October 1968. 7. Corrosion Science. Heath and Company. Vol. 10. K. Vol. 13. "On the SoCalled Linear Polarization Method for Measurement of Corrosion Rates". [ I l ] ASïM.. R..B. Handbook on Corrosion Testing and Evaluation. Materials Protection. Vol.C. p. Water Research Center External Report TR 241. Standard Guide for Examination and Evaluation of Pitting Corrosion.G.. and Gummow.. [15] Zumdahl.J. F. Corrosion Science.B. Vol. National Association of Corrosion Engineers. NACE Conference CORROSION90 (Las Vegas). [16] Ailor. 27. Corrosion.. ASTM Specification G 587. Chemistry Experin~eni and Theory. 11. p. .G. and Oldham. October 1991. 383.33. and Parkinson. 1990. B. No..C.W. W. John Wiley & Sons. New York.No. Vol. 1989. 38311. Chemistry. Vol. S. p.H. 787. 1971. 14. [20] Townley. [23] ASTM. [18] Mansfeld.[IO] Wakelin. ASTM Specification G 10289. 1985. 1973. Standard Reference Test Method for Making Potentiostatic and Potentiodynamic Anodic Polarization Measurements.. "Corrosion of Ductile iron Pipe". D. Corrosion. Houston. "A Method for Determinhg Corrosion Rates From Linear Polarization Data". "Determination of Maximum Scan Rate for Linear Polanzation Measurements". "Corrosion Rates from Polarization Curves: A New Method". K. 47. "Cornparison of the Soi1 Corrosion Resistance of Ductile bon Pipe and Gray Cast iron Pipe". R. and Mansfeld. Corrosion. 1971. New York.S.. p. K. F. R. October 1971.. p. Proceedings of Texas. [14] Segal.B. p. [13] De Rosa.. "The Effect of Copper on the Corrosion of bon Watennains". 440.W.. paper no. No. United Kingdom. [21] Oldham.. 10. D. E. p. ASïM Specification G 4694... 10. October 1986.A. John Wiley & Sons. 1958. . [17] Oldham. [12] Sears.. M. Standard Practice for Calculation of Corrosion Rates and Related Information fiom Electrochemical Measurements. 813. [19] Stem. 434. 737. and Mansfeld. P. F . "A Modification of the StemGeary Linear Polarization Equation". Massachesetts.
[31] Coben. N. National Association of Corrosion Engineers. Psychological Bulletin.. 1982. Vol. paper no. paper no. [25] Stroud. p.R. Volume 1. SAS Institure bc.. .. Texas. H. and Smith. and Peck. Applied Muhivariate Statistics for the Social Sciences.C.. 585. J. "A Power Primer". 4.. p. 411. [27] Draper.F.Then and Now". p. J. 1993. 1996. SAS Institue Inc. SAS / STAT User's Guide. Volume 2. "Corrosion Control Measures for Ductile Iron Pipe".. Houston. New Jersey. Proceedings of NACE Conference CORROSION93 (Las Vegas). Houston.H. Lawrence Erlbaum Associates. Texas.. [28] Montgomery. 1. John Wiley & Sons. D. [30] SAS Institute. 1992. (261 Stevens. No. 155. 112.. 1966. J. Introduction to Linear Regression Ana!vsis. John Wiley & Sons. E. New York. Version 6. 1990. 58511.. New York. T. Proceedings of NACE Conference CORROSION93 (New Orleans). "Evaluating Soil Corrosivity . Applied Regression Anaiysis.A..[24] Fitzgerald III. North Carolina. Mahwah. 1993. 1990. National Association of Corrosion Engineers. Version 6. North Carolina. SAS / STAT User's Guide. [29] SAS Institute.
Equation A. 0 0 T = 298 Kelvin. r [h. .2: R = 8. The reduction of Zn is represented by the following equation: The Nerst potential is obtained by substituting the appropriate values into the following equation: = +$ + 2.APPENDM A: DERIVATION OF POTENTIAL EQUATIONS A.and [ared] = [Zn(s)] = 1. Once the above values are substituted. because the concentration of a solid is equal to 1.] = [zn2'] . F = 96500 C Ieq.314 Jldeg mole.1 Equation for + N .2 becomes: hZn = hZnO + 0.d] (A4 For the reduction of Zn.059212 * log [zn2+] .303 RTInF * log [a&[a. the following values are substituted into Equation A. n = 2 electrons transferred.
Equation A.d] = [cu2'] .2 Equation for 4~h.059212 * log [CU*'] .2 becomes: hcu = hcuO + 0.303 RTInF * log [a.2) For the reduction of Zn.d] (A. [h. F = 96500 C Ieq. r T = 298 Kelvin.] [a. The reduction of Cu is represented by the following equation: The Nerst potential is obtained by substituting the appropnate values into the following equation: + N = c " + 2.A.. = [Cu(s)] = Once the above values are substituted.. because the concentration of a solid is equal to 1.c.2: R = 8. n = 2 electrons transferred. the following values are substituted into Equation A.3 14 Jldeg mole.]I[a.and 1..
J/[a.log [H+]. i.d] = [ p l 2 .303 RT/2F * log [ P l 2 / 1 Furthemore. and = partial pressure of Hz(g) = 1 atm.. Equation A.2) ' . h pH = ..e.] [a. Once the above values are substituted. because the reduced species is a gas under normal pressure.A. + O = 0.. given the following two facts: a a reduction of H+ is taken as the baseline potential.2 becomes: h= ~ H + O + 2. [a.3 Equation for eNB+ The reduction of H+ is represented by the following equation: The Nerst potential is obtained by substituting the appropnate values into the following equation: = +d + 2.2: For the reduction of H O n = 2 electrons transferred for each Hl released. the following values are substituted into Equation A. and the fmal equation becomes: ..d] 64.303 RTInF * log [a.
The standard deviation of the concentrations obtained for each calibrating solution are then compared to the maximum values permitted: 1. 0.40 mV. the average potential is plotted versus the known chlonde ion concentration.APPENûIX B: TESTING FOR CHLOFUDE ION CONCENTRATION B. the concentration is equal to 0. The measured potential of the soil sample is located on the curve and the corresponding concentration is obtained either fiom the equation.2.2.5 for 0. and 1. e curve which fits the five data points best is an exponential one. 0.82 % From Equation B.816 % the From the curve. For example. The chloride ion concentrations of the soil samples tested are obtained from the curve or from the equation in Figure B.2.1622 e The choice of which method to use depends on the degree of precision required.01%. 1. and 1. 7 .3%. 0. such as the one presented in Figure B. This is done a minimum of two times.1 Creating a Concentration vs. The equation of this curve is presented in the upper nght hand corner of Figure B. the concentration is approximately equal to 0. potential curve is to record the potentials of five calibrating solutions of known concentration: 0. For each calibration solution. and a curve.0 for the remainimg solutions. for a potential of following concentrationsare obtained: a 0 . is obtained.2.33%. or from the cuve itself.01%. = 0.65%. . and the average potential for each calibrating solution is calculated. An example of the potentials obtained during a calibration exercise are presented in Figure B.03%. Potential C u w e The first step in creating a concentration vs.
1 Poteotisls Obtained for Calibrsting Solutions: Series 1 . 0 1 Figure B.1995 JK01ïû JK82 Trial 1 Trial 2 Trial 3 Trial 4 Trial 5 Trial 6 Trial 7 Trial 8 Tria1 9 Trial 1 0 'ALUES TO BE PLO'ITED: Potential (mv) Chloride Concentration (%) 51.2 7 0 .03 0 .9 40.3 34.33 0.LECïRODE: JACQUESCARTIER ATE: AhWLES: MAY 26. 3 0.65 0.8 16. 1 1 .
2 Calibration CUNCfor Stries 1 . Figure B .SERIES 1: Chloride Concentrationvs Potential Chbilde Conunmfhn ( 7 4 94.
APPENDiX C : TRIALS FOR REPRODUCIBILITY Trial nins were performed on the various soil samples in order to establish a complete procedure for testing subsequent soil samples. The corrmion rate was obtained twice. Each test is composed of two parts: the Tafel test from which the values of P. through two independent sets of tests. indicating that the procedure followed yields reproducible results. are obtained. The results indicate that the corrosion rate of a metal sample placed in soi1 No.1 19 mm/yr. The results of each test are presented in Figures B. 123 is presented for analysis.1 and Trial No.6.2. Soi1 sample No. and the Liear Polarization test from which the corrosion rate is obtained. 123 is equal to 0. . As it can be seen. the results obtained fiom the hvo trial runs are very sirnilar. and P. This result was obtained fiom both Trial No.3 through B.
TafelCuve 'jkl23tLdia' 27n1199512:59:34 Figure 8.1 :Llnear Polarkation Raulb .4 Trial No.3 Trial No. 1 :Tafel Results Figure 8.
2 Tafel Results Figure B. 2 :Linear Polarhtion Rnults .5 Trial No.6 Trial No.Figure B.
quantiles including the median.1 Data Exploration Prior to begiming statistical analysis of the data using sophisticated computer packages and advanced statistical techniques. variance. etc. mean. it is vely important to be familiar with the data set. and the nomal probability plot . a 9 stemandleaf diagram and boxand whisker plot. and includes the follouing: Data exploration Simple Iinear regression analysis Data transformation Multiple variable regression Categorical data Outliers Variable Selection Mode1 Validation Power The SAS Statistical Package D. Each variable should examined individually. skewness. and the following quantities should be obtained for each 126291 : a the usual descriptive statistics: number of data points.APPENDlX D: PRINCIPLES OF REGRESSION ANALYSIS This chapter presents the techniques used in a n a l m g the data presented in Chapter 3: Procedures and Apparatus. standard deviation.
they provide considerable information about the data. and plays a key role in selecting the number of variables that will make up an equation. or are they spread out? Are there any values that are remarliably different form the general trend? Quantiles are also used to calculate the range outside which a value is considered an outlier. quantile ranges and outliers quick and easy. it makes the calculation of the quantiles.) provide considerable information about the range of values of a given variable.g. and the standard deviation of a variable are easily calculated.l. the number of data points. are constmcted with the values of a given variable.Quantities such as the number of data points. The identification of outliers is extremely important in statistical analysis. It is necessary to calculate the power of a statistical test. They are also the values that will be needed in subsequent calculations. etc. upper and lower hinges. such as the those presented in Figure D. is a quantity that plays an important part of almost every statistical calculation: it is used to determine significance in the ANOVA table. Stemandleaf diagrams. the mean. which is usually more easy to understand [26291. and can help sumrnanze the distribution of the data in a visual way. N. Furthermore.Leaf by IO**1 Figure D. Stem Leaf 16 14 12 10 8 6 4 2 O 0 2 4 6 8 10 12 14 16 6 61 36 679 01148 O 0033683 2345 75 8497 87 900866 e 1 2 2 3 5 1 7 4 2 4 2 6 2 1 2 30 O 80 5 1 1 S ++++ nnltiply Stem. e. Are the values al1 within a limited range. The quantiles obtained (median.l Stem and LeaiDiogram .
Stem Leaf 16 14 12 IO 8 6 6 61 36 679 01148 O 0023683 2345 75 8497 87 900866 30 O 80 S 1 2 2 3 5 1 7 4 4 2 O 0 2 4 6 6 10 12 14 5 16 5 **++ 2 4 2 6 2 1 2 1 1 Uultiply Srem. A box and whisker plot is illustrated in Figure D.2.It is almost always a good idea to display numerical information graphically where it is possible. but it contains more information than its ofien needed. The box and whisker plot aims to display the elementary information (median. 2 Stem and Leal Dingram and Boxplot . The s!ernandleaf diagram is an excellent tool for the graphical display of the distribution of the data.Leaf by 101 Figure D . hinges and outliers) pphically 126291.
distributed nomally. The plot should resemble a straight line if nonnality is tenable 126291. The observaticns are arranged in an increasing order of magnitude and then plotted against expected normal distribution values. Figure D. Normal Probability Plot Figure D .The normal probability plot is a graphical display that permits the analys! to determine if the data values art.3 shows a normal probability plot. 3 Normal Probabiliîy Plot .
X. and e. liear regression analysis is the action of fining a straight l i e to the data.2 Simple Linear Regression Analysis In simple tenns. The goal is to denve an equation that will link the values of xi and y. For each value xi observed. Figure D of Y vs. (D.=(Po+P~x.e.D. is the portion of y. ei.. predicted by the straight line. The term pi represents the slope of the straight line. The term Yaxis. Y. where (p. X. the values of e. that the straight l i e fails to predict. i. and an independent variable. Simple regression analysis involves a dependent variable.1) + Pi x. i. which is the error or the residual.e. ) is the portion of y.. The method most commonly used to calculate the Y PO O I 0 magnitude of the error of the equation. with the least . How determine if can the one line Po represents the intercept. It is our goal to fhd the line which runs through these points such that the vertical distances between the line and the y values are miniiized. is to add the squared values of each of the individual error. X Plot x. the value of y at the point where the straight line meets the represents a good esthate of the relationship between X and Y ? The answer lies in the study of the residuals. X . 4 Y vs. are minimized. The equation relating the values of each observation of y and x of the following fom: y.)+e. there is a correspondingvalue of y. This is better understood graphically. This value Figure D . 4 shows a plot amount of error possible.
it has been assumed that the variable X has an infiuence on the value of Y. and the standard error of the estimate. S2 variance [26291. but studied closely.and PI. Lx =the sum of the x values for the N observations. Ly = the sum of the y values for the N observations. and Lx2= the sum of the x2 for the N observations. can have an enormous effect on the value of SSE and. other quantities are computed to determine the measure of fit of a line. It is. y' = the mean of the y values. is simply the square root of the . The variance of the estimate.?(N2)}. N = the number of observation of x and y. consequently. on the best fit line. It is not always the case that a variable X provides any information about the behavior of the variable Y. L(xy) = the sum of the product of x and y for the N observations. represents the average of the squared errors {L~. the effect of the larger values are emphasized. .2) It should be noted that when the errors are squared. and an equation has been chosen which includes the variable X.is referred to as the Error S m of Squares. The result of this is that outliers. For the case when the line is to be chosen such that the SSE is minimized. important that outliers not be ignored. there exist a closed form solution for the parameters P. Up to this point. Syh. therefore. Besides SSE. or SSE: SSE = z e. given by 126291: where x' = the mean of the x values. whose residuals are high.2 P. The outliers will be discussed later.
y'. The value of the error sum of squares is referred 10. the horizontal line. For example. A measure of fit that is very cornrnonly used is the squared multiple correlation. as SSY. and ranges between O and 1. in the case of this model only. to as the benchmark model. i. .e. This last model is referred where Po is equal to y'. R2.10 means that taking X into consideration in predicting Y will result in a 10 % decrease in the error sum of squares. R2 = 0.5 illustrates such a case. how can one determine if the Figure D.e. is very small or PI. even insignificant. In fact. The equation relating X and Y using the benchmark model based only on the mean value of y. R' is calculated as follows [26291: R ' = SSYSSE SSY P.Figure D. a 10 % irnprovement in the prediction of Y. It will not always be so obvious that a variable X is insignificant in predicting Y. i. is the following: . The slope of the line.6) The value of R2 is always positive. This value represents how well a model predicts Y in cornparison to the benchmark model. to the SSE of the model bfised only on the mean value of y. 5 Example of an Inaignilicant Predictor variable X is significant? This is done by comparing the SSE of the mode1 including X. the straight line which best represents the points seems to be the horizontal line which runs through the mean value of y. So.
F=l is considered the baseline performance. N. This will result in a large Fratio. this signifies that almost no significant . The investment made can be compared to the variables added to obtain a better prediction. ' R the Fratio is a measure of the improvement of one model over another. considering that this improvement is compared to a model which is based on nothimg but the mean. then the benchmark model is the one that contains XI and X 2 . and the model to be tested is the one containimg al1 three. A model being tested can be compared to any model that is a submodel of itself. The value of the Fratio is calculated as follows [26291: The ideal situation is a large drop in the SSE accompanied with a small &op in the degrees of freedom. This simply means that the model being tested is an extension of the benchmark model. It is preferable that fewer variables be added and. Pnor to introducing the Fratio. the significance of a model m u t be determined by taking into account the number of variables added. however the Fratio takes into account the number of variables that were added to obtain this improvement. The degree of fieedom of a model is equal to the number of observations. rather than if this return were obtained firom an investment of $1000. If the ratio is close to 1. this benchmark model will be termed the wmodel. From this point onward. Like . 1s the improvement important enough to consider the variable X significant? This significance is determined by examinimg another important parameter in statistics: the Fratio. it should be mentioned that the benchmark model used in this computation does not have to be based only on y'. it is certainly bener if an investment of $100 yielded a retum of $10 000. minus the number of parameters k i n g fined by the model. For example. This is done by including the degrees offeedom in the equation. it does not appear to be such an important improvement.However. For example. if it is required to 3 can be added significantly to a model which includes prove whether or not a variable X the variables XI and X 2 . and the model beiig tested as the Qmodel. as such.
or ANOVA table.e.e.improvement was made.l shows the critical values of F that m u t be obtained in order to consider the Rmode1 significant. The term df error refers to the degrees of 6eedom of the Rmodel. and the value of SylX ' value is obtained by obtained by taking the square mot of the mean squares. i. Table D. there has been no return on the investment made.6 ANOVA Table . If the Fratio calculated is larger than the appropriate critical value. difference model. Figure D. The degrees of 6eedom and SSE of the wmodel. are obtained by subtracting the entries of the Rmode1 6om those of the omodel. The R dividing the SSE of the Diffmode1 by the SSE of the wmodel. the Rmode1 is considered significant 126291. and SylX.and check al1 the relevant information at a single glance is the analysis of variance table. The term df for Numerator refers to the &op in the degrees of 6eedom in going 6om the wmode1 to the Rmodel. A tool that is used to allow the analyst to quickly calculate the values of R ' . i. The ANOVA table permits rapid calculation of the relevant parameters. and presents the information in an organized format. and the Rmode1 are entered into the table. The mean squares (MS) for each model are can be obtained by dividing the SSE by the degrees of 6eedom. (1) DOF (Diff) = DOF(R) DOF(w) (2) SSE (Diff) = SSE(R) SSE(w) (3) MS (DIFF) = SSE @IFF)IDOF @FF) (4) MS ( 0 ) = SSE (n) I DOF ( n )   ( 5 ) MS (w) = SSE (w) 1 DOF (a) (6) F = MS (DIFF) 1 MS (R) (7) R ' = SSE O F F ) 1 SSE (O) Figure D. The degrees of 6eedom and SSE of the Diffmodel.6 shows a typical ANOVA table. and the Fratio is obtained by dividing the MS of the Diffmode1 by the MS of the Rmodel. F.
l Critiral Values for 194 .Table D .
Table D . l (cont'd) Critical Valucs for FI2'] .
Table D . l (cont'd) Critical Values for F '261 196 .
Table D . l (cont'd) Crincal Values for F 1261 .
When a model is being tested for significance. with a mean value of zero and a standard deviation of a . the next step is to determine if this model is significant. A normal distnbution has a mean of zero. Again. PI. when al1 the individual residuals. A tool which is very helpful in determining normality is the normal distribution plot. then we cannot depend on the results obtained from the test. the y values are normally disiribuied. with only 20% of the residuals falling outside of O f 20.8. the normal probability plot is a useful tool in determining normality ofthe y values. they must exhibit normality.7. l Figure D . and a standard distnbution of O. Figure D. e. with a mean value of zero and a standard deviation of a . Le.. the y values must be distributed normally for each value of x.3 Data Transformations Linear regression is used to calculate the bestfit equation relating a set of x variables to a set of y variables. Ifthese assumptions do not hold true. As it can be seen in Figure D. and e. 7 Normal Distribution r For each individual x value. . are determined.1. Po.9 shows an example of data failing to meet this criterion.D. n i e following fhree assumptions m u t be checked [26291: r The set of residuals for al1 x values are normally distributed. Once this equation is obtained. as discussed in Section D. are ordered and ploned. there are certain assumptions that m u t be checked in order to ensure that the result obtained is credible. As it can be seen in Figure D.
However. which would link the two phenomena.8 Normally Distributed Y values  Figure D.Figure D.9 Y Values Not Distributed Normally r The residuals are distributed independenrlyfrom one another. . This staternent implies that the behavior of the residuals independent fiorn one another. Most commonly. there is another factor not yet accounted. e. this is not ofien true.g. the reason that one point has a high residual has nothing to do with the fact that another point value has a high residual.
where xi becomes llxi: usually for physical measurements.The first two assumptions usually go hand in hand. becomes arcsinedxi: usually for proportions. the key to a simple. etc. the (a) Figure D.lOb and D. X Distribution relationship between X and Y is a linear one. . or both.lOa ldeal Y vs. Furthermore. either of the x variable. with an appropnate transformation most relationships can be made linear. Other transformations include the following 126291: reciprocal. however. where xi becomes log{ x 1 (1x) 1: usually for proportions. where x. this is not often the case. linear regression cannot be used.lOc. the data must be nonnegative. such as those presented in Figures D. When the raw data is received. The most commonly used transformation is the logarifhrn of the data. arcsine. effective transformations is the knowledge of the phenomenon being studied.: usually for fiequencies. a square root. When a nonlinear relationship exists. Forhmately. Ideally.lOa. The ideal situation is that the plot resembles the one presented in Figure D. if necessary. where no O or 1 values are present. It is generally ageed that the data that responds best to this transformation is the data representing physical magnitudes such as weight. and log odds. Any data can be manipulated to eventually appear linear. length. However. or the y variable. If one holds tnie. where xi becomes dx. Y is usually ploned versus X and the characteristics of the resulting cuve are studied. temperature. concentration. usually the other will as well. with values which are not very close to zero.
lOb.Figure D.c Nonlinear Relalionsbips Behveen X and Y .
PI X.Po .D . This lengthy calculations are reserved for s o h a r e packages such as the SAS. multiple regression can be thought of as fitting a line through a set of points in a three dimensional space. and the SSE. and two or more independent variables. and the intercept O. W. X2. The equation relating Y to the X's is of the following form: YI= Po + PI XII + B 2 x12+ . Y. The independent variables considered to best predict gas consumption are the weight of the automobile (W). The concepts presented in Section D. the SSE is a measure of the accumulated error of a model predicting Y.8) The value of the error sum of squares.. This can be best explained using an example: n i e gas consumption (Y) of 45 automobiles ir studied. In multiple regression.  Pli x.The following results were obtained: . The residual can be thought of as the distance in the ydirection between a point in space and the line. etc. The analyst m u t determine which of the two variable best predicts the gas consumption. 4 Multiple Variable Regression Multiple variable regession involves one dependent variable. or one of a higher dimension.+ PL. and the automobile length (L).. The analyst begins by obtainiig the equation.9) The parameters of the equation are obtained easily by making use of certain basic principles of matnx algebra. XI. As in simple regession.k )2 0. . (D.. and whether or not both variables should be used together. SSE is calculated accordig to the following equation: SSE = Z (y..X A + e.l on simple linear regession also apply to multiple variable regression. which will be introduced in a later section.I  xa . Although more difficult to visualize. of al1 the possible combinations of L. SSE is used to determine which combination of variables best predicts Y..
The next step is to compare the twovariable model with the three variable model to determine if . The first step is to decide between the onevariable model. the analyst must decide whether or not adding a variable produces a decrease in the SSE which is significani. It is obvious that the lowest SSE is obtained for the model in which al1 three variables are involved. The best twovariable model is the one consisting of weight + intercept. because it has the smaller SSE. The following ANOVA table shows al1 the relevant information: The Fratio obtained is larger than the critical Fratio. the best (and only) threevariable model is the one consisting of al1 three variables. However. Finally. This will alwqw be the case. 2 Inlormation about Possible Models The results indicate that the best onevariable model is the one consisting of only the weight.Table D. and the twovariable model. the twovariable model is retained. therefore the addition of the weight is significant and so therefore.
of the variance in Y that can be explained by the variable X.ll. It sliould be noted. This concept is called multicollineari/y.e. If each of the two circles is of unit area.the variable L is significant. The conclusion would have been that the model consisting of automobile length and the intercept was the best model. Conversely. that the onevariable model containimg only the intercept had been used initially.69 0.45 < F n i e Fratio obtained is smaller than the critical Fratio. the second one may provide almost as much information. . The following ANOVA table shows al1 of the relevant information: Difference Intercept + W + L (R) Intercept + W (a) 1 42 43 1 29 30 1 0. the shaded area is very small. ~ the ~ propoition . or R ~ i. therefore the addition of L is not significant. An explanation to the significance of the various models follows. Figure D. it seems easy to understand that only one of the two variables will be needed in the model. but in the absence of this variable.l l a shows the case of one independent variable. and it can be bener understood with the aid of the following Vem diagrams presented in Figures D.70 . the answer would have been affirmative. it would have been noted that it would not be so. When two dependent variables. the larger is the shaded area. the shaded area represents R*. and checked whether is was significant to add L to the model. Continuing the exercise to check whether adding W to the twovariable model would be significant. provide redundant information. as W is in this case. This means that the best model to predict gas consumption is the one containing only weight and the intercept. One of the two might be bener than the other. such as L and W. In the case when X is insignificant in predicting Y. 1. X. the higher the correlation between X and Y.
. proportion of the variance of Y accounted for by X2. with XI partialled out.1 lc. The ideal situation is to have high correlations . This value is called the squared multiple correlation. R ~ ~ . includiig the dependent and the independent variables.1 l b shows the case when two independent variables are involved. is equal to the total shaded area. ~The . Figure D. It is referred to as the squared partial correlation of X2 with Y and with X I partialled out.Figure D.is easy to see that the less XI and X2 overlap.3.ll Venn Diagrams lor 1 and 2 independent variables'16' A good tool for examinimg the extent of overlapping is to shidy the correlation matrix of a set of variables. is indicated by the shaded area in Figure D. R ~ . . Xi and X2. One such matrix is presented in Table D. It . and the larger is the proportion of Y accounted on an overall basis [261. the higher the usefulness of each of the two variable. This represents the extra information that X2 provides when Xi is already in the equation. ï h e total proportion of the variance in Y that can be explained by the two variables.
3 Correlation Matrix D. e. or negative) ? This is obtained by "expanding" the categorical variable into an appropriate number dummy variables. sulfide content (positive. The variable Soilgpe is a categorical variable with the following classes: sand. and to have low correlations between the X variables themselves. In the present form.g.between the Y variable and each of the X variables. clay. Parameters such as the mean. and sand/clay. This will most probably result in a large part of the variance of Y being accounted. categorical variables such as this one must be "expanded" into a set of dummy variables. The number of dummy variables to be created will depend on the number of classes. e. Le. the variable cannot be studied in the same way as the discrete variables. in the two variable case. in this case three classes exist and the analyst can choose to use either two or three variables. the dummy variables will assume the following values [261: . and SSE can be calculated for such variables. But how can this be achieved for categorical variables which represent a category instead of a specific quantity. a large growth in R' as each of the variables is added to the model. and a linear equation can be determined.5 Categorical Variables The techniques studied so far take only discrete variables into account. standard deviation.g. Discrete variables represent a specific quantity. clay. soiltype (sand. Table D. This can be best explained with an example. For this to be possible. a pH of 7.4 or a chioride content of 4763 ppm. trace. or sand/clay).
Table D . 5 Dummy Variables for Soiltype: 3 Variable Case The difference between the discrete and categorical variables is the effect they have on the final equation relating Y to the X's. the following overall equation would result (for the mode1 with three dummy variables): n i e variable pH has an effect on both Po and P i . i. In the three variable case. and the dummy variables will assume the following values: Sand SandIClay Clay 1 O O O O O 1 O 1 Table D . the class 'clay' is considered the reference category against which the behavior of 'sand' and 'sandklay' are assessed. For example. 4 Dummy Variables for Soiltype: 2 Variable Case In this case. For example. for a sand the equation would become: CorrRate = (Po + Pr) + Pi pH 0. However.11) . the dummy variables cm be viewed as having a direct effect on only the intercept because they assume a value equal to O or 1.e. no reference category exists. on the intercept and the dope of the l i e . if the discrete variable 'pH' and the categorical variable 'soilSpe' are used to predict the variable 'CorrRate'.
clay. . The first type of outlier can be identified by always listing the data and checking to ensure that the data has been entered accurately. References 29 and 30 should be consulted for M e r information on these techniques.. without the outlier. or are very different 6om the rest of the data. Other techniques are also available. and P. represent the jumps resulting 6om a sandlclay and D . to weak when the outlier is included. These methods did not prove to be useful in this project. This is particularly true for the regression techniques. R. The technique of creating dummy variables for coding categoncal variables is used to extend the use of multiple regression analysis to include variables that could not be included othenvise. P.In essence. but could be beneficial in future research on the subject. in case B the relationship changes 6om strong. They can occur because of two fundamental reasons: (1) a data recording or entry error was made. The amount of time it takes to list and check the data for accuracy is well worth the effort. and not to be highly influenced by just one or two errant points f261. e. This is quite important. Figure D. respectively.12 shows graphically how the inclusion of an outlier can drastically change the interpretation of the relationship between X and Y. interaction variables. but there is a strong relationship with the outlier. because the results of the statistical analysis m u t reflect most of the data. Statistical procedures in general can be quite sensitive to outliers. Similarly. 6 Outliers Outliers are data points that split off. or (2) the subjects are simply different 6om the rest. and nonlinear combiations relating x and y. In case A. the term p. Outliers can have a very large effect on the correlation coefficients. and the computer time is minimal.. representç the 'jump' in CorrRate resulting 6om the soi1 being a sand.g. Convenely. It is very important to be able to identify outliers and then decide how to consider them. there is no relationship without the outlier.
12 Eîîert olOutliers on R ' [261 .Figure D.
Therefore.=the standard deviation of the observations of variable j. That is. outliers can be detected by studying z scores. = the recorded value of observation i for variable j. which if deleted. and a . they do not fit the model well. The Z scores can also be calculated for the residuals obtained when a model is fitted to the data. then z scores with absolute values near 3 should be considered as potential outliers. the prediction equations with and without the point are quite different. Xj. Of course. have been considered. A quantity that measures this change is the Cook's distance (CD). These standardized residuals are used for fmding observations whose predicted y values are quite different from their actual y value. can produce a substantial change in at least one of the regression coefficients. about 99 % of the scores should lie withii three standard deviations of the mean. Up to this point. any z score value larger than 3 indicates a value very unlikely to occur. the z score can be calculated as follows: (D. Cook and Weisberg (1982) indicate that a . the above rule is generally considered reasonable lZ6'. This is because. it may be reasonable to expect a few subjects to have z scores of over three.. As in the previous case. Cook's distance measures the combined effect of a point being an outlier on Y and on the set of predictors. However. pJ= the mean value of the observations of variable j. Altematively. x . = the z score of observation i for variable j. i. Unlike the z scores which identi6 the outliers on Y or on the X's individually. in a distribution which is normal. If the variable is approximately nürmally distributed.Besides the graphical method. an outlier can be defmed as a point. an observation whose standardized residual is greater than three in absolute value is considered an outlier 1261. 12) where z. For each variable being studied. the measurement cf the outliers on the predictor variables. if the number of observations is large (Say >100).e. then simply by chance.
D. However. needs to be considered. if. which were introduced in Section D. the prospects of cross validation may be influenced negatively. Furihermore. If too many variable are used. which should be included in a model. it is important for the investigator to be judicious in the selection of predictors. The analyst can exercise hislher judgment in the creation of new variables fiom the existing ones. Once the outliers are identified. the analyst knows that two different variables essentially measure the same thing. Outliers should not necessarily be regarded as 'bad'. if none of these appear to be the case. However. . An alternative is the removal of one of the variables fiom the set. it has been argued that outliers can provide some of the most interesting cases for further research [261. but report two analyses (one including the outliers and the other excluding it). then it is legitimate to drop the outlier. then one should not drop the outlier. Most ofthe methods of model selection are strongly based on the concept of multicollineanty and semipartial correlations. Prior to introducing the techniques for mode1 selection. for example. a new variable may be created by averaging them. if one fin& after further investigation of the outlying points thzt an outlier was due to a recording or entry error. As a matter of fact. a decision m u t be made on whether or not the errant point should be eliminated fiom the set. or by adding the z scores of the two. ïhis action m u t not to be taken lightly. and without serious consideration.4. the appropriate correction should be implemented and the analysis m u t be repeated with the corrected data. and would therefore identify probable outiiers [261. > 1 would generally be considered too large. if the errant data is due to an instrumentation error. it mus1 be emphasized that the single most important tool in selecting a subset of variables for use in a model is the knowledge of the area under study. then of coune.7 Variable Selection The number and type of variables.CD.
The automobile example of Section D . a test is made for the least useful predictor.A quantity which measures the extent to which a variable provides redundant information is the variable infIationfactor ( VIF). 4 is a good example of the fonvard selection procedure. The methods most commonly used to select a mode1 are the forward.4. backward and stepwise selection procedures. At each step. it is not removed [261. and the correlation is obtained. as was obtained in the ANOVA tables presented in Section D. The first predictor that enters the equation is the one with the highest simple correlation with y. In the forward selection procedure. it provides redundant information. A high correlation indicates that the remainiig X variables account for a large amount of the variation in the variable under study. It is suggested that a variable be removed if VIF > 10. The importance of each predictor is constantly reassessed. If this predictor is significant. a given predictor will not be significant and the procedure will be terminated. which is based on the calculation of the correlation between the independent variables only Each independent variable is regressed in tum against the remainimg X's. or held Through the use of semipartial correlations. This means that the variable provides little information that the remaining variables do not already provide. i. Variables should be eliminated one at a tirne. constant. and the new VIF values should be calculated prior to the removal of any subsequent variables [261. etc. At some point. the predictor wiîh the largest semipartial correlation with y is considered.e. at each stage ofthe procedure. The backward selection procedure involves the removal of predictor fiom an equation initially containing al1 the predictors. However. and a predictor that may have been the best entry candidate earlier may now be superfluous. the correlations among the predictors are disentangled and the unique variance of each predictor related to the variance of y is determined. the partial Fratio is calculated for every predictor. The smallest value is compared to the critical Fratio. and is removed. and . once a variable enters the equation. The stepwise procedure is basically a variation of the forward selection procedure. Al1 these procedures involve examining the contribution of a predictor with the effect of the other predictors partialled out.
The forward. For this reason. and chooses the model(s) where C. and the process continues until al1 insignificant variables are removed. threevariable models. ultimately it is the knowledge of the researcher of the phenomena under study that will ensure that the best and the most reasonable model is selected. The new equation is computed. k. the stepwise procedure is considered the best of the three methods because it verifies al1 of the variables at each step and removes the one(s) that are redundant. where p = k+l. Mallows' Cp is given in the output file created whenever a SAS program is used to propose a model [16'. Another criterion often used is Mallows' C. For these models. A mistake that is commonly made by analysts is to consider the final mode1 proposed by these methods as the besr model possible. It n i e analyst can then compare behveen the various combinations with high R2 values. but simply lists the 10 best combinations of onevariable..the appropriate variable is removed. It is generally agreed that the number of variables. n. This is not the case. In general.e. in the data set. This measure was introduced by Mallow (1973) as a criterion for selecting a model. and is free to use hisher judgment is selecting the = p. twovariable. measures the total squared error. However. the amount of underfitting andor overfitting is minimized. there are neither too many nor too few predictors in the equation. It is suggested that al1 the of above methods be examined individually prior to deciding on a final model. these methods are limited in their use. etc. The rule of thumb proposed is to chose k such that n/k > 10 [261. This technique does not propose a model. . i. The model proposed may be just one of the many models which provide the best prediction for Y.. ranked according to their overall RZ value. to be included in an equation depends on the number of observations. The one technique that appears to offer the analyst with the most choice in the model is the Rsquare procedure. most reasonable model. stepwise and backward selection procedures do not necessarily propose the sarne final model.
the line was not fined to this particular point prior to computing the error. computing the adjusted R2. This is done for each of the n observations. and then applied to the other set of data. versus what it would be in the population as a whole using the same equation. Certainly the equation will not predict as well. the y value for each observation is set aside and a predictive equation is denved with the remaining data. and the percentage of decrease is noted in many cases. The adjusted R ' value of the population is compared to the R2value of the sample. One can still obtain a good measure of the predictive power by the use of the PRESS statistic bredicted residual sum of squares). Unlike the SSE. the PRESS statistic is more representative of the true error because the equation of the line was obtained without the observation under study. Le. the validation data. and the PRESS statistic. n prediction equations are derived and n true errors are determined.e. and the correlation between the two sets is calculated. The PRESS statistic is simply the sum of the squares of these errors. Shrinkage refers to the decrease in R~as it is measured in the sample with the equation derived 6om it. in this approach.D. i. The regression equation is denved using the socalled derivation data (2/3). i. . The predicted values of y for the validation data are compared with the recorded y values.8 Model Validation It is cmcial for the researcher to obtain some measure of how well the regression equation will predict on an independent sample of data. This correlation rrpresents how well the equation works on an independent sample of data I z 6 ' . would work on the population sample.e. The adjusted R2value estimates how well a prediction equation derived from one sample. Data splitting involves randomly splitting the available data into two parts (roughly 113 and 213). there is not enough data to permit random splitting. The adjusted R' value measures the shrinkage in predictive power. It does not indicate how well the denved equation will predict for the other samples 6om the same population. can the equation be generalized? There are essentially three ways of validating a model: data splitting. the theoretical sample consisting of al1 possible data points. and as a result.
but they are inversely related. For example.e.which is the probability of accepting the nul1 hypothesis when it is false. if a researcher is going to invest a lot of time and money in canying out a study. significance was not found even though it may have been there. and as such. Depending on the circumstance.e. i. . Not only can either of these errors occur. however. then he or she would certainly want to have a hi& power. power analysis can be undertaken before or after the data has data has been collected and analyzed. fmding a variable to be significant.O5 or . when in fact it is not 12& 311.P.O1 to rninimize the probability of making that kind of error. i. If the power was low.e. it is not. The a level set by the experimenteris a subjective decision. 9 Power is the probability of rejecting the null Type 1 error. another type of error that can be made in conducting a statistical test: type II error. 6 Relationrhip behveen a. and Power '26' The entries in the last column. i. a high probability of finding what they are looking for if it is really there. fmding a variable to be significant when it is. finding a variable to be significant when in fact. Le. if a researcher has already cornpleted a study and has found that a certain variable is insipificant. it is important to know whether or not the power was high enough. (1.P). denoted P. There is. A low power may lead the research to make false conclusions about the significance of a variable [261. or the level of significance (a) hypothesis when it is m e . An example of the twogroup problem with 15 observations follows: Table D . but it is usually set at . is called the power of the experiment.D . the chances of fmding significance may have been too low. Altematively. and it is the probability of rejecting the null hypotheses when it is false.
the power of a test for different values of n is presented in Table D. i. and The effect size. power is rarely a problem. c The sample size n. . The power of a statistical test depends on the following factors ['? The a level set by the experimenter.5). The equation relating the sample size n. the effect size of phenomena are considered medium. In general. Power is heavily dependent on the sample size.e. . when present. The effect size is usually classified as small (f large (f ' > 3. 13) F where L is a parameter which depends on the a value chosen. the difference in the number of variables between the Rmodel and the omodel (k~).8 for a = .O5 ["l. is very easy to detect. or A large effect size is usually associated with a phenornenon which.05. the effect size f . For example.is ['Il: n = L+K+l (D.and on the power of the statistical test.5) ['Il. medium (f ' = 1. for a medium effect size and an a = . a 0. to what extent is the effect ofthe variable observable. L is obtained by consultingtables ruch as Table D. Table D . It is only when small sample sizes are evaluated that power cm influence the results obtained. and the number of variables in the Rmodel K.2). when a sample size is large. 7 Relationsbip between n and Power lZ6l As the above example suggests.7.
it is suggested that both volumes be consulted to fully understand the scope of this statistical package. It can be used for a veIy wide range of analyses. Stmcturally. ** *O *O It is very widely distributed. a SAS program is composed of three fundamental blocks: the staternents setting up the data.10 The SAS Statistical Package The Statistical Analysis System (SAS) was selected for use in this project because126. Essentially. the data lines. D. For a list of the procedures and a complete description.e. the SAS program reads a file created by the analyst and performs the ** various analyses requested. and It is a well documented package. having been in development and use for over two decades.301. VOLUME 1 and 2 [29.It is generally considered tme that a sample size of 50 or Iarger is sufficient to detect a medium effect. and becorne familiar with al1 of the possible techniques that may be used to analyze the data. fiom very simple statistics to complex multivariate analyses.301. However. The most preferred volume in this project is VOLUME 2 which contains the fundamental regression procedures. . and a series of procedure (PROC) statements which describe the statistical analyses to be performed on the data entered 129. the power of the test would be approximately 0. it is suggested that the reader refer to two volumes: the SASISTAT USER'S GUIDE.70. i.2%301. It is easy to use.
8 Values of L for a = 0.Table D .5 13'] .