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Blossoming technique can be used to obtain penetrations into the environment construction and variableness of organic affair. One of import, technique is fluorescence slaking which involves a lessening in organic affair fluorescence emanation strength by externally added extinction agent ( Szarka et al. , 1994 ) . The ensuing lessening in fluorescence emanation strength can be measured and related straight to the slaking agent concentration via different slaking theoretical accounts. Previous work in biological scientific discipline has been utilizing fluorescence slaking technique to find halide and metal ion concentrations ( Lakowicz, 1999 ; Badugu et al. , 2004 ; Brege et Al, 2007 ) due to both the sensitiveness of fluorescence measurings and the simpleness of the slaking reaction method employed by the Stern-Volmer relationship. However the complexness of steady province fluorescence slaking mechanism generates troubles in its reading, and the extinction informations do non follow the criterion additive Stern Volmer look due to the incidence of other procedures beside dynamic slaking doing divergences and nonlinearity in the informations behaviour ( full inside informations will be presented in litreature ) . Therefore, there is a demand to execute fluorescence slaking theoretical accounts in a systematic manner to get the better of some of the jobs that generates from assorted informations behaviour in order build a baseline cognition on the impact of the intervention procedure ( i.e. disinfection via chlorination ) on the organic affair fluorescence strength of drinkable H2O, the nature of the residuary fluorescence signal, and therefore the suitableness of fluorescence quenched technique as a monitoring tool in H2O intervention plants.

Modeling fluorescence quenched informations can be classified by the theoretical account used and by the intent of the analysis. The most common theoretical account used is the standard additive Stern Volmer equation and a modified signifier of the equation is used when either positive or negative divergence from one-dimensionality occur on the quenched information. In add-on, the behaviour of the fluorescence quenched informations gives an indicant of the efficiency of fluorescence quenched and the possible formation of non fluorescence composites during reaction clip. Examples of the methods used for fluorescence extinction theoretical accounts found in the literature ( subdivision thirty ) .

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The mechanism of Cl slaking organic affair in aqueous solutions is non good understood ( Korshin, 1999 ; Giri, 2003 ; Beggs et al. , 2009 ) during chlorination, disinfection by merchandises ( DBP ‘s ) signifier when organic affair reacts with an oxidant/ germicide ( i.e. Cl ) the varying degrees of DBP ‘s ( such as THM ‘s ) are formed depending on the features of organic affair, Cl dosage, pH, temperature and reaction clip ( Liang and Singer 2003 ; Roccaro et al ; 2008 ; Miller et al. , 2009 ) taking to hold an affect on the fluorescence signature of satisfied informations. This chapter, aims to research the fluorescence slaking theoretical accounts associating experiments that have different mixture of slaking decay to the steady province criterion Stern Volmer equation and look into how fluorescence slaking theoretical accounts can be used to track alterations in organic affair feature and the possible formation of DBP ‘s during chlorination.

7.2. The Ksv value construct and the Stern Volmer Equation

Knowledge of the value Stern Volmer invariable is of involvement, enabling the survey of alterations in the chemical construction of organic affair and therefore its fluorescence belongingss. Quenching reactions can be by and large classified as either inactive or dynamic procedures or a combination of both. Inactive extinction can be attributed to the formation of non fluorescent land province complex compounds where the fluorophore can organize a stable composite with another molecule. Whereas, dynamic extinction occurs when the excited fluorophore experiences contact with an atom or molecule that can ease non-radiative passages to the land province without the formation of complex ( Lakowicz, 1999 ) .The reading of a alteration in the quenchability ( i.e. the lessening or increase in fluorescence strength ) can be expressed by alterations in slaking changeless value the standard Stern Volmer relationship which is consistent with either inactive or dynamic extinction mechanism is used to show the fluorescence slaking informations as secret plans of ( Fo/F ) versus [ Q ] ( Lakowicz, 1999 ) .

…………………………………………………………………………………… ( 1 )

Where, Fo and F are the fluorescence strength in the absence and presence of quencher, severally. Q is the concentration of the quencher, in this instance it represents Cl consumed ( ) , and is the Austere -Volmer extinction invariable. Figure ( 1-a, B, degree Celsius and vitamin D ) shows a typical Stern Volmer secret plan, Fo/F fluorescence strength in the absence and presence of quencher versus [ Q ] Cl consumed for the 4 WTW ‘s, Initial chorus girl concentrations ( 2.1, 1.7, 1.3, 1, 0.5 mg/l ) , over 2 hours reaction period. Quenching informations are expected to hold a additive relationship, a additive austere Volmer secret plans indicate that all fluorophores are every bit accessible to the quencher. In order to cipher the Stern Volmer invariable for the same information presented in Figure ( 1-a, B, degree Celsius and vitamin D ) additive arrested development ( least square fit method ) was applied to all the fluorescence quenched informations, Figure 2 shows an illustration of using least square fit method for informations of Draycote WTW ‘s the consequences of value and correlativity coefficient are summarized in Table 1-a, B, degree Celsius and d. Generally the consequences indicate that a lessening in initial Cl concentration leads to a lessening in. The R2 value is comparatively good, nevertheless, its interesting to detect that R2 explore the low values at high and low initial Cl ranges i.e. for 2.1 and 0.5 mg/l. of the 5 H2O intervention works, Strensham fluorescence quenched informations can be seen to hold the most high value scope between ( 0.99+/- 0.0004 for 2.1 mg/l and 0.82 +/- 0.0021 for 0.5 mg/l ) , this is likely to be due to the type of H2O holding an intermediate organic affair character with low measured TOC 4.24 mg/l and accordingly low sum of Cl consumed. Whitacre fluorescence quenched informations exhibited value between ( 0.96+/- 0.0081for 1.7 mg/l – 0.66 +/-0.0029 for 0.5 mg/l ) this is due to the character of organic affair holding high microbic organic affair, high Cl consumed and high measured TOC 4.98 mg/l in comparing to Strensham WTW. For Melbourne fluorescence slaking informations the scope of value was between ( 0.88+/-0.007 for 2.1 mg/l – 0.42 +/- 0.0019 for 0.5 mg/l ) holding high measured TOC 7.33 mg/l. for Draycote fluorescence quenched informations the nature of organic affair construction ( hydrophilic ) with high measured TOC 8.09 mg/l consequence in a big sum of Cl consumed, accordingly take downing the scope ( 0.58+/-0.0009 for 2.1 mg/l – 0.325 +/- 0.0026 mg/l ) . Interestingly, Bamford fluorescence slaking informations did non exhibit any alteration in fluorescence ratio during the 2 hours reaction, Once chlorinated a rapid lessening in fluorescence strength occurred and the Fo/F ratio stabilized during 2 hours of reaction therefore, it was non able to obtain values for this site. This is likely to be due to the type of H2O being ( hydrophobic rich ) and a less reactive organic affair output to a slow Cl consumed ( Beroza, 2009 ) . Overall, the values of the slaking invariables appears to follow a tendency depending on initial Cl concentration and organic affair character hence, at 2.1 & A ; gt ; 1.7 & A ; gt ; 1.3 & A ; gt ; 1 & A ; gt ; 0.5 mg/l. In add-on the values of slaking changeless elucidate the reaction type between the organic molecule and the quencher ( i.e. high values of slaking changeless reveal that fluorescence strength informations is expeditiously more satisfied at high Cl concentration, meanwhile low slaking changeless indicate that non all the organic molecules interacted with the quencher due to low initial Cl concentration and rapid decay of Cl ( Cl & A ; lt ; OM ) this explains the high values of deliberate experimental mistake of deliberate criterion mistake scope +/- 0.0021 -0.0029 for 0.5 mg/l low Cl concentration, whereas a cut down in experimental mistake occurs at high initial Cl concentration 2.1 mg/l, calculated standard mistake scope +/- 0.0004- 0.0009, see appendix ( x ) for deducing the mistake analysis equation and Postpone Angstrom shows an illustration of ciphering the experimental mistake for Draycote WTW.

Recent surveies have began to measure how fluorescence spectrometry may be used to measure organic affair responsiveness and imitate DBP ‘s formation during organic affair chlorination surveies such as peak strength excitement -emission braces ( Marhaba and Kochar, 200 ; Chen and Valentin, 2007 ) every bit good as the emanation wavelength that corresponds to half the maximal fluorescence strength 0.5 ( Fabbricino and Korshin, 2004 ) and correlated theses step to DBP formation. Likewise ( Rocaro et al. , 2009 ) use transmutation in fluorescence strength at specific wavelength during chlorination to foretell DBP formation. A possible restriction of these methods, show that Cl interruptions down the active aromatic construction in humic molecules into smaller compounds switching the location of coveted strength readings and perchance increasing strength in some readings ( Fabbricino and Korshin, 2004 ) giving wrong indicant of fluorescence slaking mechanism ( this will be explained more in chapter look intoing slaking mechanism ) . Furthermore, the features of organic affair which can be divided into fractions of hydrophobic and hydrophilic. Hydrophobic fraction consist of preliminary humic and fulvic acids with high molecular weight, being less reactive which yield to low Cl consumed. Whereas, hydrophilic have low molecular weight ( proteins and amine acids ) which were found to be more likely to respond with Cl ensuing in high DBP formation ( Gang et al. , 2002 ; Miller et al. , 2009 ) . It was shown that by using the standard Stren Volmer relationship and the finding a important information can be obtain on the alterations in organic affair construction through different scopes of chlorination. Besides an addition in value can be correlated to a lessening in DBP ‘s formation ; this is in understanding with observations from laboratory trial runned on the same set of satisfied informations bespeaking the fact that during chlorination organic affair experience two sorts of slaking mechanism both ( inactive and dynamic ) . Strensham WTW had the high values ( 0.99 – 0.89 ) with a low norm of THM ( 24.37 – 9.25ug/l for 2.1 and 0.5 severally. Whereas Draycote WTW informations had the lowest scope of value with high THM norm ( 40.37- 32.55 ) for 2.1 and 0.5 severally ( farther work on relationship between slaking and THM formation will be discussed in chapter ten ) .

7.3. Predictive Equations

7.3.1. Modified Stern Volmer equation

As noted earlier, the value of can be determined by mensurating the fluorescence strength at different quencher concentrations utilizing standard additive Stern Volmer equation. However, the steady province fluorescence slaking informations do non follow the criterion additive Stern Volmer look. This is likely due to chlorine ingestion, formation of non fluorescence composites and some mistakes accrue within the analysis ( see appendix for mistake analysis finding ) . Consequently the gradient of best fit line for the correlativity of Stern Volmer equation does non go through through the intercept 1 on the y-axis, which one would anticipate as ( the fluorescence strength in the absence of quencher / fluorescence strength in the presence of quencher is equal to one ) when Cl ingestion is zero. Therefore, an attack has been developed to the usage of Stern Volmer application in order to get the better of some of the jobs and let directly forward application with comparatively good truth during the usage of fluorescence slaking technique on different beginnings of H2O intervention works. The developed theoretical account will connote restraining the correlativity such that the line of best tantrum base on ballss through the intercept one, Figure ( 3-a, B, degree Celsius and vitamin D ) can be seen in for Draycote WTW for scope of Cl concentration2.1, 1.3, 1. and 0.5 mg/l, shows the best fit lines with one line non fitted through intercept one, and the other fitted through intercept one. The method will merely hold a somewhat consequence on value of the gradient line and in some instances a somewhat alteration in the correlativity coefficients R2 e.g. for chlorine concentration 2.1mg/l the exhibited a somewhat lessening in value from 0.58 to 0.56 for lines ( non fitted and fitted through the intercept 1 ) severally, with the correlativity coefficient being the same R2 0.94 Figure 3-a. While, for chlorine concentration 0.5 mg/l somewhat increase in values from 0.325 to 0.330 for lines ( non fitted and fitted through the intercept 1 ) severally Figure ( 3-d ) . Although the developed method had a somewhat consequence on the values of. The overall correlativity of with initial Cl concentration had similar tendencies to the observed correlativity when using the criterion line drive Stern Volmer equation ( non fitted through the intercept ) for each of the 5 WTW ‘s with different magnitude bespeaking that this developed method does do n’t deteriorate the standard Stern Volmer relationship, and tantrums for the intent.

7.3.2. Sphere of action slaking theoretical account

In old subdivision fluorescence extinction of organic affair by assorted Cl scope and Ksv value has been investigated by steady province additive Volmer relationship. However in some instances, it has been observed that experimental informations show a divergence ( either positive or negative ) from one-dimensionality ( Lakowicz, 1999 ) . The positive divergence ( upward curvature ) is attributed to assorted procedures such as formation of non fluorescence composite and intersystem crossing, whereas negative divergence ( down curvature ) occur when the fluorophores are non every bit accessible to the quencher i.e. one being accessible to quencher and the other unaccessible to quencher and a modified Stern Volmer equation was used to derive information about the most accessible fluorophore residue ( Laws and Contino, 1992 ) , a different theory suggested that Cl consumed over class of reaction, and many of the C atoms in OM will non decently take part in redox reaction specially if the Cl concentration was low and decay quickly, which moderately explains the negative curve toward the x-axis in the ascertained informations as the fluorescence strength starts to retrieve after a period of clip when low Cl concentration decay ( Korshin et al. , 2000 ) ( a more elaborate account will be in chapter slaking mechanism ) . In Figure ( 1-a, B, degree Celsius and vitamin D ) of 4 WTW ‘s at that place appear to hold a non one-dimensionality divergence upward curvature secret plan for high Cl concentration 2.1 and 1.7 mg/l and a downward curvature secret plan at low Cl concentration 0.5 mg/l, this gives an indicant of the presence of parallel slaking procedure taking topographic point beside dynamic slaking mechanism ( Thipperudrappa et al. , 2007 ) . Such divergence has been observed by research workers ( Knutson, 1992 ; Laws and Contino, 1992 ; Szarka et al. , 1995 ; Lakowicz, 1999 ; Geddes, 2001, Giri, 2003, Thipperudrappa, 2006 ) proposing that in instance the steady province fluorescence slaking informations do non follow the stander additive SternVolmer relationship, a modified Stern Volmer equation for the nonlinear divergence can be applied in order to derive more information on the insight reactions between the quencher and organic affair. For fluorescence quenched informations exhibiting an upward curvature secret plan the domain of action inactive extinction theoretical account ( Lakowicz, 1999 ) will be applied to the experimental informations

…………………………………………………………… ………….. ( 2 )

Where W is a map of quencher concentration Q. Harmonizing to this theoretical account, inactive extinction occurs if the quencher molecule is really close or in contact with the fluorescent molecule at the exact excitement minute, and this was interpreted by the fact that merely a certain fraction ( e.g. W ) , of the aroused province molecules are really quenched by collisinoal mechanism. However, some molecules in the aroused province which is ( 1-W ) are deactivated about after being formed because of the randomly positioned quencher which interact strongly with the aroused province molecules organizing dark complex compounds.

The extra fraction W is expressed as ;

( 3 )

Where V is the inactive extinction invariable, and represents an active volume component environing the fluorophore in its aroused province.

Frank and Wavilow, 1931 suggest that inactive slaking mechanism occurs in a indiscriminately distributed system, when a quencher happens to shack within a domain of action environing the fluorophore upon its excitement province. The chance of the quencher being within this volume at clip of excitement depends on the volume and quencher concentration. Assuming that the quencher is indiscriminately distributed in solution, so the chance of inactive extinction is given by Poisson distribution. W is a map of quencher concentration Q, hence depends on the quencher concentration. For high slaking efficiency the austere Volmer secret plan by and large will divert from its one-dimensionality accordingly Equation ( 2 ) can be expressed in the followers,

………………………………… ………… ( 4 )

In instance when VQ & A ; lt ; =1 ; W ? ( 1-VQ )

……………………………………………… ( 5 )

W=1- [ V*Q ] …………………………… ……………………………… …… …….. ( 6 )

Figure ( 4 ) shows an illustration for secret plan of versus for chlorine concentration 2.1mg/l Draycote WTW. From the additive arrested development method the values of the incline ) and the intercept ( V ) has been determined for the initial Cl concentrations Table 2-a, B, degree Celsius, and d summarized the consequences of for all the 4 WTW ‘s. It ‘s interesting to advert that a general comparing between the deliberate values of utilizing both the criterion linear and modified Stern Volmer equation will non be applicable as the value in the modified Stern Volmer equation will affect the value of slaking changeless with regard to dynamic slaking changeless in this instance the value of W ( Szarka et al. , 1994 ) , while value in the standard Stern Volmer equation will stand for the association invariable of the complex formation by intending the presence of parallel slaking procedure both inactive and dynamic ( Thipperudrappa et al. , 2006 ) . Finally for the negative Stern Volmer divergence which occur for low Cl concentration, & A ; lt ; = 0.5 mg/l as stated a modified Stern Volmer equation was used to derive information about the most accessible fluorophore residue. On a survey by Wyatt et al. , ( 1987 ) an experiment was conducted on three halide detectors slaking tryptophan residues in protein to derive information about the most accessible residues utilizing a modified Stern Volmer equation. nevertheless, Lakowicz, ( 1999 ) revealed that the usage of the modified Stern Volmer method for negative curvature will supply a arbitrary consequences throughout using the method on a information for ( Lehrer, 1978 ) and ciphering the false categories of tryptophan residues quenched by iodide. Consequently, for the intent of this survey merely standard additive Stern Volmer equation will be applied for fluorescence quenched informations of initial Cl concentration & A ; lt ; = 0.5 mg/l.

7.4. Performance of prognostic extinction theoretical accounts

To supply a better apprehension of the best fit theoretical account to stand for the fluorescence quenched informations, the three theoretical accounts ( model 1standard additive Stern Volmer, theoretical account 2 the modified criterion additive Stern Volmer ( fitted through the intercept1 ) and model 3Sphere of Action ) were tested through using the deliberate Ksv value to find the predicted Fo/F and a comparing between the deliberate ( Fo/F ) values and the experimental information was taken topographic point based on Root Mean Square Error ( RMSE ) method which imply choosing the most fit theoretical account depending on lower RMSE value. Table 4 and Figure 5-a, B, degree Celsius and vitamin D, show an illustration of plotting the deliberate predicted values of Fo/F for models1, 2 and 3 among the experimental information for Draycote WTW, Table 5. From the artworks, and the deliberate values of RMSE of the 5 initial Cl concentrations for each H2O intervention work Table 3-a, B, degree Celsius and d. Results showed that for high Cl concentration 2.1 and 1.7 mg/l, theoretical account 3 Sphere of Action is more likely to stand for the quenched informations holding RMSE 0.028 less than RMSE ( 0.052and 0.047 ) for both model 1 and 2 severally within a difference of ( 46 % ) suggesting that for high initial Cl concentration the Sphere of Action model 3 will be more consistent when ciphering the predicted values and slaking changeless this is in understanding with ( Thipperudrappa et al. , 2007 ) proposing the at high quencher concentrations positive divergence would detect and experimental information is sooner to be analysed by utilizing Sphere of Action inactive extinction theoretical account. For chlorine concentrations 1.3, 1 and 0.5 mg/l, the value of RMSE for theoretical account 1 and 2 is less than RMSE for theoretical account 3 for Strensham, Whitacre and Melbourne and Draycote. Overall, it can be seen that theoretical account 2 will be more consistent when ciphering the predicted values and slaking invariables for 1.3, 1 and 0.5 mg/l, this indicates the theory of the presence of inactive slaking even in the absence of a curvature secret plan ( Lakos et al. , 1995 ) which explains why RMSE of theoretical account 3 in some sites e.g. in Draycote RMSE value, is either equal or somewhat more than value of RMSE model 2 corroborating the hypothesis of the theoretical account 2 ability to foretell the alterations in organic affair construction during chlorination.

7.5. Decisions

A basic apprehension of fluorescence extinction theoretical accounts for chlorinated drinkable H2O is a requirement to develop baseline cognition on the alterations in organic affair character during chlorination. Furthermore, the possibility of developing a straightforward theoretical account stand foring conditions of fluorescence extinction. Therefore, in chapter 7 the consequence of different slaking theoretical accounts in stand foring the fluorescence quenched informations was investigated. It was shown that the changeless extinction value Ksv give a important information on quantitative and qualitative alterations in organic affair construction through different chlorination conditions and H2O types. Ksv value for 2.1 & A ; gt ; 1.7 & A ; gt ; 1.3 & A ; gt ; 1 & A ; gt ; 0.5 mg/l Cl concentration, for different type of H2O Ksv value varies depending on H2O quality beginning as for Strensham WTW the Ksv value high scopes ( 0.99-0.82 ) due to its intermediate organic affair character, low TOC and low Cl ingestion, while Draycote WTW ‘s exhibited the lower scope of Ksv ( 0.58- 0.325 ) due to H2O beginning comparatively hydrophilic, high measured TOC concentration and high Cl demand. Whitacre and Melbourne were in between exhibiting Ksv scopes ( 0.96-0.66 ) and ( 0.88-0.42 ) severally. Interestingly Bamford WTW showed a different attack the Ksv value was non calculated as the fluorescence organic affair exhibited rapid slaking one time chlorinated afterwards the Fo/F ratio remains changeless during 2 hours of reaction. This is likely to be due to the type of H2O ( which is hydrophobic rich ) and less reactive organic affair which output to a slow Cl ingestion. Besides it was found that Ksv values can be used as preliminary index of THM formation and to compare between different sites possible THM formation ability e.g. Draycote WTW with low scope of Ksv value exhibited high norms of measured THM and for Strensham WTW with high scope of Ksv values, low norms of measured THM. Furthermore, the ability of three slaking patterning methods ( standard line drive Stern Volmer equation, the modified criterion line drive Stern Volmer equation line fitted through the intercept 1 and Sphere of action ) to find the Ksv value and predict the Fo/F was tested.

Overall, the modified criterion line drive Stern Volmer ( equation line fitted through the intercept 1 ) and Sphere of Action theoretical account provided the best analysis in foretelling alterations in fluorescence belongingss during chlorination. Although the standard additive Stern Volmer theoretical account has been reported to qualify alterations in fluorescence quenched informations for different applications, here it was found to be less robust. And the developed theoretical account 2 is more consistent when ciphering the predicted values and slaking changeless.

Figure 1.a: Typical Stern Volmer secret plan, peak C fluorescence strength in the absence and presence of quencher versus Cl consumed. For Draycote station GAC H2O samples Initial chorus girl concentrations ( 2.1, 1.7, 1.3, 1, 0.5 mg/l ) , over 2 hours of reaction at clip intervals ( 5, 15, 30, 45, 60, 120 proceedingss ) .

Figure 1.b: Typical Stern Volmer secret plan, peak C fluorescence strength in the absence and presence of quencher versus Cl consumed. For Strensham station GAC H2O samples Initial chorus girl concentrations ( 2.1, 1.7, 1.3, 1, 0.5 mg/l ) , over 2 hours of reaction at clip intervals ( 5, 15, 30, 45, 60, 120 proceedingss ) .

Figure 1.c: Typical Stern Volmer secret plan, peak C fluorescence strength in the absence and presence of quencher versus Cl consumed. For Whitacre station GAC H2O samples Initial chorus girl concentrations ( 2.1, 1.7, 1.3, 1, 0.5 mg/l ) , over 2 hours of reaction at clip intervals ( 5, 15, 30, 45, 60, 120 proceedingss ) .

Figure 1.e: Typical Stern Volmer secret plan, peak C fluorescence strength in the absence and presence of quencher versus Cl consumed. For Melbourne station GAC H2O samples Initial chorus girl concentrations ( 2.1, 1.7, 1.3, 1, 0.5 mg/l ) , over 2 hours of reaction at clip intervals ( 5, 15, 30, 45, 60, 120 proceedingss ) .

Figure 2 ; A typical Stern Volmer secret plan, Fo/F for humic like fluorescence strength in the absence and presence of quencher ( free Cl consumed ) of Draycote WTW using the least square fit method. Initial concentrations ( 2.1, 1.7, 1.3, 1, 0.5 mg/l ) , over 2 hours of reaction at clip intervals ( 5, 15, 30, 45, 60, 120 proceedingss ) .

Figure 3.a ; A typical Stern Volmer secret plan, Fo/F by using theoretical account 1 ( non fitted through the intercept ) and Model 2 ( additive tendency line fitted through 1 ) for 2.1 mg/l, Draycote WTW.

Figure 3.b ; A typical Stern Volmer secret plan, Fo/F by using theoretical account 1 ( non fitted through the intercept ) and Model 2 ( additive tendency line fitted through 1 ) for 1.3 mg/l, Draycote WTW.

Figure 3.c ; A typical Stern Volmer secret plan, Fo/F by using theoretical account 1 ( non fitted through the intercept ) and Model 2 ( additive tendency line fitted through 1 ) for 1 mg/l, Draycote WTW.

Figure 3.d ; A typical Stern Volmer secret plan, Fo/F by using theoretical account 1 ( non fitted through the intercept ) and Model 2 ( additive tendency line fitted through 1 ) for 0.5 mg/l, Draycote WTW.

Figure 4 ; the relationship between [ 1- ( F/Fo ) ] / [ C ] V F/Fo for initial Cl concentration 2.1 for Draycote WTW.

Figure 5.a ; A comparing between the experimental information ( observed informations ) and model 1 standard Stern Volmer equation, theoretical account 2 modified Stern Volmer equation and theoretical account 3 Sphere of Action theoretical account. Initial chlorine concentration 2.1 mg/l over two hours reaction period, Draycote WTW.

Figure 5.b ; A comparing between the experimental information ( observed informations ) and model 1 standard Stern Volmer equation, theoretical account 2 modified Stern Volmer equation and theoretical account 3 Sphere of Action theoretical account. Initial chlorine concentration 1.3 mg/l over two hours reaction period, Draycote WTW.

Figure 5.c ; A comparing between the experimental information ( observed informations ) and model 1 standard Stern Volmer equation, theoretical account 2 modified Stern Volmer equation and theoretical account 3 Sphere of Action theoretical account. Initial chlorine concentration 1 mg/l over two hours reaction period, Draycote WTW.

Figure 5.d ; A comparing between the experimental information ( observed informations ) and model 1 standard Stern Volmer equation and theoretical account 2 modified Stern Volmer equation. Initial chlorine concentration 0.5 mg/l over two hours reaction period, Draycote WTW.

Table 1.a: the values of Ksv Stern Volmer slaking changeless by using the standard equation and the correlativity coefficients. for the initial Cl concentrations ( 2.1, 1.3, 1 and 0.5 mg/l ) for Draycote WTW.

Cl ( mg/l )

Ksv

R2

S.E

2.1

0.58

0.94

0.0009

1.3

0.402

0.97

0.0014

1

0.392

0.98

0.0021

0.5

0.325

0.90

0.0026

Ksv slaking changeless ; Ksv.SE =Ksv * { ( mistake Fluorescence ( 0.05/ F ) + error Cl consumed ( 0.02/ Q ) }

Table 1.b: the values of Ksv Stern Volmer slaking changeless by using the standard equation and the correlativity coefficients. for the initial Cl concentrations ( 2.1, 1.3, 1 and 0.5 mg/l ) for Strensham WTW.

Cl ( mg/l )

Ksv

R2

S.E

2.10

0.99

0.95

0.0004

1.70

0.92

0.97

0.0006

1.30

0.91

0.97

0.0008

1.00

0.87

0.99

0.0009

0.50

0.82

0.74

0.0021

Table 1.c: the values of Ksv Stern Volmer slaking changeless by using the standard equation and the correlativity coefficients. for the initial Cl concentrations ( 2.1, 1.3, 1 and 0.5 mg/l ) for Whitacre WTW.

Cl ( mg/l )

Ksv

R2

S.E

1.70

0.96

0.94

0.0081

1.30

0.86

0.92

0.0009

1.00

0.81

0.91

0.0009

0.50

0.66

0.77

0.0029

Table 1.d: the values of Ksv Stern Volmer slaking changeless by using the standard equation and the correlativity coefficients. for the initial Cl concentrations ( 2.1, 1.3, 1 and 0.5 mg/l ) for Melbourne WTW.

Cl ( mg/l )

Ksv

R2

S.E

2.10

0.88

0.95

0.0007

1.70

0.87

0.93

0.0015

1.30

0.49

0.98

0.0006

1.00

0.48

0.85

0.0017

0.50

0.42

0.64

0.0019

Table 2.a ; Calculated values of slaking changeless ( Ksv ) and inactive extinction invariable ( V ) of initial Cl concentration ( 2.1, 1.3 and 1 mg/l ) Draycote WTW.

Cl ( mg/l )

Ksv

Volt

2.1

-0.178

0.495

1.3

0.6583

-0.194

1

-1.429

1.514

Table 2.b ; Calculated values of slaking changeless ( Ksv ) and inactive extinction invariable ( V ) of initial Cl concentration ( 2.1, 1.7, 1.3 and 1 mg/l ) Strensham WTW.

Cl ( mg/l )

Ksv

Volt

2.10

-0.405

0.792

1.70

0.089

0.468

1.30

0.082

0.505

1.00

0.231

0.418

Table 2.c ; Calculated values of slaking changeless ( Ksv ) and inactive extinction invariable ( V ) of initial Cl concentration ( 1.7, 1.3 and 1 mg/l ) Whitacre WTW

Cl ( mg/l )

Ksv

Volt

1.70

-0.119

0.659

1.30

-0.217

0.185

1.00

-0.559

-0.941

Table 2.d ; Calculated values of slaking changeless ( Ksv ) and inactive extinction invariable ( V ) of initial Cl concentration ( 1.7, 1.3 and 1 mg/l ) Whitacre WTW

Cl ( mg/l )

Ksv

Volt

2.10

-0.337

0.735

1.70

0.451

0.304

1.30

-0.133

0.450

1.00

0.751

-0.146

Table 3.a ; The RMSE for theoretical account 1 the criterion Stern Volmer equation, theoretical account 2 the modified Stern Volmer equation and theoretical account 3 domain of action for Draycote WTW.

Chlorine

theoretical account 1

theoretical account 2

theoretical account 3

Cl 2.1

0.0516

0.0468

0.0283

Cl1.3

0.0169

0.0169

0.0170

Cl 1

0.0129

0.0126

0.0116

Cl0.5

0.0146

0.0145

Table 3.b ; The RMSE for theoretical account 1 the criterion Stern Volmer equation, theoretical account 2 the modified Stern Volmer equation and theoretical account 3 domain of action for Strensham WTW.

theoretical account 1

theoretical account 2

theoretical account 3

Cl 2.1

0.0730

0.0816

0.0526

Cl 1.7

0.0510

0.0428

0.0286

Cl1.3

0.0456

0.0416

0.0478

Cl 1

0.0718

0.0612

0.0149

Cl0.5

0.0718

0.0612

Table 3.c ; The RMSE for theoretical account 1 the criterion Stern Volmer equation, theoretical account 2 the modified Stern Volmer equation and theoretical account 3 domain of action for Whitacre WTW.

theoretical account 1

theoretical account 2

theoretical account 3

Cl 2.1

0.0831

0.0805

0.0277

Cl 1.7

0.0669

0.0568

0.0474

Cl1.3

0.0742

0.0641

0.211

Cl 1

0.0527

0.0514

0.0734

Cl 0.5

0.0629

0.0573

Table 3.d ; The RMSE for theoretical account 1 the criterion Stern Volmer equation, theoretical account 2 the modified Stern Volmer equation and theoretical account 3 domain of action for Melbourne WTW.

theoretical account 1

theoretical account 2

theoretical account 3

Cl 2.1

0.0592

0.0533

0.0212

Cl 1.7

0.0465

0.0461

0.0503

Cl1.3

0.0182

0.0179

0.0193

Cl 1

0.0441

0.0361

0.0351

Cl 0.5

0.0469

0.0383

Table 4 ; The ascertained and deliberate values of Fo/F for theoretical account 1,2 and 3 for Cl concentrations 2.1, 1.3, 1, 0.5 mg/l Draycote WTW.

Chlorine concentration

2.1

clip ( proceedingss )

Cl consumed

observed

theoretical account 1

theoretical account 2

theoretical account 3

0

0.00

1.00

1.00

1.00

1

5

0.64

1.33

1.19

1.18

1.3

15

0.75

1.37

1.23

1.22

1.38

30

0.81

1.42

1.26

1.25

1.43

45

0.89

1.46

1.34

1.33

1.5

60

0.92

1.52

1.37

1.36

1.54

120

0.97

1.64

1.41

1.39

1.59

Chlorine concentration

1.3

clip ( proceedingss )

Cl consumed

observed

theoretical account 1

theoretical account 2

theoretical account 3

0

0

1.00

1.00

1.00

1.00

5

0.4

1.18

1.16

1.16

1.16

15

0.51

1.20

1.21

1.21

1.21

30

0.55

1.22

1.22

1.22

1.22

45

0.69

1.25

1.28

1.28

1.28

60

0.7

1.28

1.28

1.28

1.28

120

0.74

1.33

1.30

1.30

1.30

Chlorine concentration

1

clip ( proceedingss )

Cl consumed

observed

theoretical account 1

theoretical account 2

theoretical account 3

0

0.00

1.00

1.00

1.00

1.00

5

0.32

1.12

1.13

1.12

1.12

15

0.39

1.15

1.15

1.15

1.15

30

0.45

1.18

1.18

1.17

1.17

45

0.59

1.20

1.23

1.23

1.23

60

0.64

1.25

1.25

1.25

1.25

120

0.70

1.29

1.27

1.27

1.28

Chlorine concentration

0.5

clip ( proceedingss )

Cl consumed

observed

theoretical account 1

theoretical account 2

theoretical account 3

0

0.00

1.00

1.00

1.00

5

0.22

1.07

1.07

1.07

15

0.23

1.08

1.07

1.08

30

0.35

1.13

1.11

1.12

45

0.39

1.15

1.13

1.13

60

0.41

1.13

1.13

1.14

120

0.43

1.12

1.14

1.14

Appendix A ;

Mistake analysis computation

But i?¤Fo = i?¤F

i.e. , the mistake in KSV = mistake in F + mistake in Q

= ( ) + ( )

The mistake finding Cl is 0.02, therefore =0.02. The mistake in finding fluorescence is known to be 0.05 nm, therefore = 0.05. The Ksv is the slaking changeless for each initial Cl concentration. utilizing the equation of deliberate mistake in Ksv ; = Ksv * [ ( + ( ) ] , mistake would use for each point, Ksv +/- norm of Ksv

Postpone A ; the computation of standard mistake analysis and values for Cl concentration 2.1, 1.3, 1 and 0.5 mg/l for Draycote WTW.

2.10

Q

0.02/Q

F

Fo/F

0.05/F

§Ksv= ( Ksv* ( 0.02/F+0.05/F )

§Ksv*100

§Ksv*100/KSV

0.00

# DIV/0!

82.00

1.00

0.00

0.64

0.03

61.54

1.33

0.00

0.0186

1.86

3.21

0.75

0.03

60.00

1.37

0.00

0.0160

1.60

2.75

0.81

0.02

57.69

1.42

0.00

0.0148

1.48

2.56

0.89

0.02

56.15

1.46

0.00

0.0136

1.36

2.34

0.92

0.02

53.85

1.52

0.00

0.0131

1.31

2.27

0.97

0.02

50.00

1.64

0.00

0.0125

1.25

2.16

1.48

2.55

South dakota

0.0022

0.22

0.39

Selenium

0.0009

0.09

0.16

1.30

0.00

# DIV/0!

81.54

1.00

0.00

0.40

0.05

69.23

1.18

0.00

0.0201

2.01

5.07

0.51

0.04

67.69

1.20

0.00

0.0159

1.59

4.00

0.55

0.04

66.92

1.22

0.00

0.0147

1.47

3.71

0.69

0.03

65.38

1.25

0.00

0.0118

1.18

2.98

0.70

0.03

63.85

1.28

0.00

0.0117

1.17

2.94

0.74

0.03

61.54

1.33

0.00

0.0111

1.11

2.78

South dakota

0.0035

0.35

0.88

Selenium

0.0014

0.14

0.36

1.00

0.00

# DIV/0!

81.54

1.00

0.00

0.32

0.06

73.08

1.12

0.00

0.0248

2.48

6.32

0.39

0.05

70.77

1.15

0.00

0.0204

2.04

5.20

0.45

0.04

69.23

1.18

0.00

0.0177

1.77

4.52

0.59

0.03

67.69

1.20

0.00

0.0136

1.36

3.46

0.64

0.03

65.38

1.25

0.00

0.0125

1.25

3.20

0.70

0.03

63.08

1.29

0.00

0.0115

1.15

2.94

South dakota

0.0052

0.52

1.32

Selenium

0.0021

0.21

0.54

0.50

0.00

# DIV/0!

81.54

1.00

0.00

0.22

0.09

76.15

1.07

0.00

0.0298

2.98

9.16

0.23

0.09

75.38

1.08

0.00

0.0285

2.85

8.76

0.35

0.06

72.31

1.13

0.00

0.0188

1.88

5.78

0.39

0.05

70.77

1.15

0.00

0.0169

1.69

5.20

0.41

0.05

72.31

1.13

0.00

0.0161

1.61

4.95

0.43

0.05

73.08

1.12

0.00

0.0153

1.53

4.72

South dakota

0.0065

0.65

2.00

Selenium

0.0026

0.26

0.82

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