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by using statistical experimental design

Nihal Bursali a , Suna Ertunc b , Bulent Akay b,∗

a Yenimahalle Municipality Precidency, 06170 Yenimahalle, Ankara, Turkey

b Ankara University, Faculty of Engineering, Department of Chemical Engineering, 06100 Tandoğan, Ankara, Turkey

Received 22 April 2005; received in revised form 10 January 2006; accepted 28 February 2006

Available online 30 March 2006

Abstract

The purpose of this study was to determine the effective operating parameters and the optimum operating conditions of a batch saponification

process in the frame of the process improvement. Full two-level factorial and face-centered central composite (FCCC) statistical experimental

design methods were used successively. Examined parameters were the main and interaction effects of temperature, agitation rate, initial sodium

hydroxide (NaOH) and ethyl acetate (EtOAc, CH3 COOC2 H5 ) concentrations. Selected process response was the fractional conversion rate of

NaOH (XA ). Temperature and agitation rate were found to have no effect on the response at the 10% selected significance level (α = 0.1). The

dependence of response on the NaOH and EtOAc concentrations was illustrated by a linear second-order polynomial model. Examination of the

residuals served as a diagnostic check of the model and it was found that the model was good enough to fit the experimental data. Optimum

operating conditions at which maximum XA was obtained about 100% were found to be 0.01 mol L−1 NaOH and 0.1 mol L−1 EtOAc by applying

response surface method (RSM). With the use of residual analysis and statistical techniques, more reliable and proper results were obtained at the

process improvement stage of the saponification process.

© 2006 Elsevier B.V. All rights reserved.

Keywords: Process improvement; Statistical experimental design; Response surface methodology; Saponification reaction; Residual analysis

1. Introduction ence. Carr et al., applied statistical program planning for process

improvement to reduce the process development time by apply-

Experimentation is made to determine the effect of the inde- ing fractional factorial design [3]. Lind et al. applied response

pendent variable (factor) on the dependent variable (response) surface methodology (RSM) and full two-level factorial design

of a process and a relation between them illustrated by a regres- to a chemical process in which antibiotic was produced [4].

sion model by using experimental data. Statistical design of Xu et al. used statistically based experimental designs for the

experiment (DOE) is a well known efficient experimentation medium optimization of an important medical microorganism

technique and has been applied in a wide range of fields such as [5]. Andersons, applied design of experiments technique to the

drug and food industry, chemical and biological processes, etc., problem of preparing microwave popcorn [6]. More studies are

to produce high quality products, to operate more economical available in e-journals [7,8].

process, to ensure more stable and reliable process [1,2]. The There are a lot of DOE methods and the selection of them

studies including application of DOE methods have been made is made according to objectives and the number of examined

for more than 40 years and the advance of DOE applications has factors [2]. The objectives of the experiment can be classified

been assisted by the developments in the field of computer sci- as screening, comparing and applying RSM. Screening exper-

iment is applied to determine the most effective factors on the

process response. RSM is generally used to find the optimal con-

Abbreviations: ANOVA, analysis of variance; DOE, statistical design of dition by using quadratic polynomial model and it is applied in

experiments; CCC, central composite circumscribed design; CCI, central com- consequence of a screening experiment.

posite inscribed design; EtOAc, ethyl acetate; FCCC, face-centered central

composite design; RSM, response surface method

In this study, the hydrolysis process of an ester called ethyl

∗ Corresponding author. Tel.: +90 312 2126720; fax: +90 312 2121546. acetate (EtOAc, CH3 COOC2 H5 ) in an alkaline condition was

E-mail address: bakay@eng.ankara.edu.tr (B. Akay). examined in terms of process improvement. As it is well known,

0255-2701/$ – see front matter © 2006 Elsevier B.V. All rights reserved.

doi:10.1016/j.cep.2006.02.010

N. Bursali et al. / Chemical Engineering and Processing 45 (2006) 980–989 981

the hydrolysis of a fat or an oil in alkaline condition produces This irreversible reaction is a second-order overall but first order

soap for cleaning purpose and the reaction is called saponifica- with respect to each reactant and rate expression is given by Eq.

tion. The reaction which occurs in the alkaline condition is also (2):

called saponification. Thus, the hydrolysis of EtOAc to produce

sodium acetate (CH3 COONa) and ethyl alcohol (C2 H5 OH) by −rNaOH = −rEtOAc = kCNaOH CEtOAc (2)

using NaOH is called saponification reaction, although the end

In this reaction, hydroxyl ions are consumed and acetate ions

product is not soap. When the related literature on the alkaline

are produced. Since hydroxyl ions are more conductive than the

hydrolysis of EtOAc is searched, it is observed that there are

acetate ions, a decrease in the conductivity is observed as the

not so many studies on the process improvement stage of this

reaction progresses. The change in conductivity is used to mon-

process. Previously published studies are generally related to

itor the alkaline hydrolysis of EtOAc. Based on this principle,

kinetics of this reaction [9].

a relation between the conductivity of the reaction mixture and

Although esters are not soluble in alcohol, water and in

NaOH concentration is obtained as given below [11]:

similar solvents, the salt obtained at the end of the saponi-

fication reaction is soluble in such kind of solvents. This C − C∞ CNaOH − CNaOH∞

= (3)

property is important in view of the usage area of carboxylic C0 − C ∞ CNaOH0 − CNaOH∞

acid salt obtained at the end of the saponification reaction.

Sodium acetate, obtained as an end product in this study, is since,

a commercially important carboxylic acid salt, is used in a

CNaOH∞ → 0 as t→∞ (4)

large area in industry such as petrol, cosmetic, textile, paint

etc. It is used to remove the insoluble calcium salts in textile, Eq. (3) is rearranged and given in Eq. (5):

to intensify the color of paint in paint industry and is used in

food industry being as a tampon and protector. It is also used CNaOH C − C∞

= 1 − XA = (5)

as a tampon in haemodialysis and leather industry and used in CNaOH0 C0 − C ∞

the neutralisation of mineral acids. By considering commercial

The relation between reaction rate and XA is given by Eq. (6):

and industrial importance of this process, optimum operating

condition and operating factors effects were examined for this CEtOAc0

process to obtain high purity end product, to operate more −rNaOH = kCNaOH CEtOAc = kCNaOH0 (1− XA )

2

XA .

CNaOH0

economical and reliable process. (6)

In this work, statistical design of experimental method was

applied on the hydrolysis process of ethyl acetate in an alkaline

condition. This study focused specifically on the improvement of 2.2. Experimental apparatus

this hydrolysis process. The optimal condition was determined

and the factor effects were investigated. In this study a bench-top batch reactor (Armfield CEM-liquid

This study based on experimentation consists of two stages: phase chemical reactor, Hempshire, England) with temperature,

screening experimentation and applying RSM. Screening exper- flow rate and agitation rate control units was used as given

imentation aimed to find the most important factors and it was schematically in Fig. 1. Two-liter mixed batch reactor was used

planned according to full two-level factorial experimental design with 1.5 L working volume. Temperature was controlled by cir-

method. Fractional conversion rate of NaOH (XA ) was selected culating hot water through a coil immersed in reactor.

as response. All possible factors thought to have an effect on

the response and their levels were considered at the brainstorm- 2.3. Analytical methods

ing stage of the study and it was decided to examine the main

and interaction effects of the temperature (◦ C), agitation rate The conductivity of the NaOH was measured by using WTW

(rpm), initial NaOH and EtOAc concentrations (mol L−1 ) on LF39 (Welheim, Germany) type conductivity meter. The sam-

the response. Experimental results were analyzed statistically pling time was determined on the basis of the experimental

by analysis of variance (ANOVA) using Fisher’s F-ratio [1,2]. design treatments and 10 mL of reaction mixture sample was

Optimal values of significant factors were determined as taken from the reactor to measure the conductivity.

0.01 mol L−1 NaOH and 0.1 mol L−1 CH3 COOC2 H5 for 100%

of XA by obtaining response surface contours at different levels 2.4. Plan of experiments

of factors by using second-order polynomial model.

2.4.1. Screening experiment—full two-level factorial

2. Material and method experimental design

At this stage, factors were studied at their maximum and

2.1. Reaction kinetic minimum levels determined according to our experience about

the process and from the literature research. The number of

The stochiometric representation of saponification reaction

experiments for four factors was determined as 24 = 16 accord-

between EtOAc and NaOH is given by Eq. (1):

ing to full two-level factorial experimental design method

NaOH + CH3 COOC2 H5 → CH3 COONa + C2 H5 OH (1) [2,10]. To simplify the calculations, factors were studied with

982 N. Bursali et al. / Chemical Engineering and Processing 45 (2006) 980–989

their codified values. The relation between codified and natural Maximum, minimum and average levels of the factors are

values of factors is given below: codified as (+1), (−1) and (0), respectively as given in

Table 1. The center point is equal to the average value of a

Ui,natural − Ui,average factor.

Xi = (7)

U Experimental design matrix constructed according to stan-

Ui,max + Ui,min dard order rule was given in Table 2 with the codified values

Ui,average = (8) of the factors. Experiments were executed randomly to provide

2

protection against the extraneous factors, which could effect the

Ui,max − Ui,min measured response. Randomization of experiments was made

Ui = (9)

2 by using Gnumeric program of Linux operation system. In all

Table 1

Natural and codified values of factors

Natural Codified

Temperature (◦ C) 40 30 20 +1 0 −1

Sodium hydroxide concentration (mol L−1 ) 0.1 0.055 0.01 +1 0 −1

Ethyl acetate concentration (mol L−1 ) 0.1 0.055 0.01 +1 0 −1

N. Bursali et al. / Chemical Engineering and Processing 45 (2006) 980–989 983

Table 2 Table 3

Experimental design matrix for full two-level factorial design with three center FCCC experimental design matrix

points

N X3 X4 XA

N Random Standard X1 X2 X3 X4 XA

order order 1 −1 −1 0.11

2 −1 −1 0.6

1 0 0 0 0 0.847 3 −1 −1 0.36

2 1 10 1 −1 −1 1 0.946 4 −1 −1 0.65

3 2 6 1 −1 1 −1 0.1 5 +1 −1 0.1

4 3 9 −1 −1 −1 1 0.97 6 +1 −1 0.1

5 4 1 −1 −1 −1 −1 0.11 7 +1 −1 0.0

6 5 13 −1 −1 1 1 0.79 8 +1 −1 0.1

7 6 5 −1 −1 1 −1 0.1 9 −1 +1 0.97

8 7 7 −1 1 1 −1 0.0 10 −1 +1 0.95

9 8 11 −1 1 −1 1 0.92 11 −1 +1 0.92

10 0 0 0 0 0.847 12 −1 +1 0.99

11 9 8 1 1 1 −1 0.1 13 +1 +1 0.79

12 10 4 1 1 −1 −1 0.65 14 +1 +1 0.86

13 11 15 −1 1 1 1 0.9 15 +1 +1 0.9

14 12 14 1 −1 1 1 0.86 16 +1 +1 0.98

15 13 12 1 1 −1 1 0.99 17 0 0 0.85

16 14 16 1 1 1 1 0.98 18 0 0 0.85

17 15 2 1 −1 −1 −1 0.6 19 0 0 0.67

18 16 3 −1 1 −1 −1 0.36 20 −1(−α* ) 0 0.93

19 0 0 0 0 0.67 21 +1(+α* ) 0 0.55

22 0 −1(−α* ) 0.18

23 0 +1(+α* ) 0.95

experimental runs, the reaction time was considered as 5 min. To 24 0 0 0.77

estimate experimental error and to detect the quadratic effects

of factors three center point runs at the beginning, middle and

end of the 16 experiments were placed in the design matrix. In In the above equations SSeffect is called the sum of square of a

this table the last column represents the experimental data. factor effect and is calculated by using Yates’ Algorithm. SSerror

represents the sum of squares of error and it is calculated from

2.5. RSM-FCCC experimental design the replicated center point experiments as given below:

One of the RSM designs called face-centered central com- SSerror = (yC,i − ȳC )2 (13)

posite (FCCC) design was used to identify the second-order center point

polynomial model [2]. Design matrix given in Table 2 for four

factors for screening experiment was used to construct the FCCC Also center point data are used to investigate the existence of

design matrix for only two factors by augmenting adding star the curvature over the region of exploration [1,2]. For a single-

points (±α* ). “α* ” value is given ±1 for FCCC design for two degree-of-freedom, sum of squares for curvature is given by Eq.

factors [2]. FCCC Design matrix was given in Table 3. (14):

SScurvature = . (14)

The method used to compare the magnitude of estimated nF + n C

effects of factors with the magnitude of experimental error is

called analysis of variance (ANOVA). If the magnitude of a 2.5.2. Graphical residuals analysis

factor effect is large when compared with experimental error, it Graphical residual analysis is an important and efficient

is decided that the changes in the selected response cannot occur model validation test method and was used to check the ade-

by chance and those changes in the response can be considered quacy of the constructed models in this study [2]. The objective

to be the effects of the factors. The factors causing a variation in behind this method was to check the following assumptions that

the response are called significant. In this study, Fisher’s F-test made at the beginning stage of the experimental designs.

was used in the analysis of variance and given in Eq. (10):

MSSeffect 1. Errors are normally distributed with mean zero and constant

F= (10) variance.

MSSerror

2. Errors are random and distributed independently.

SSeffect

MSSeffect = (11)

d.f.1

Design-Expert 6.0.10 trial software (Stat-Ease Inc., Min-

SSerror neapolis, USA) was used in this study to examine the residual

MSSerror = (12)

d.f.2 graphics [12].

984 N. Bursali et al. / Chemical Engineering and Processing 45 (2006) 980–989

Table 4

Application of Yates’ Algorithm to determine factor effects and sum of squares

Treatment combination Y (1) (2) (3) (4) (4) ÷ 24-1 Estimate of effect (4)2 (4)2 ÷ 24 SSeffect

X1 0.6 1.01 0.3 7.35 1.076 0.134 1.16 0.0725

X2 0.36 0.2 3.82 0.88 0.43 0.054 0.185 0.0115

X1 X2 0.65 0.1 3.53 0.196 0.004 5 × 10−4 1.6 × 10−5 1 × 10−6

X3 0.1 1.91 0.78 0.2 −1.71 −0.21 2.92 0.1825

X1 X3 0.1 1.91 0.1 0.23 −0.576 −0.072 0.33 0.02

X2 X3 0.0 1.65 0.046 −0.1 −0.17 −0.02 0.029 1.8 × 10−3

X 1 X2 X3 0.1 1.88 0.15 0.104 0.216 0.027 0.047 2.53 × 10−3

X4 0.97 0.49 0.3 −1.42 5.33 0.67 28.41 1.77

X 1 X4 0.946 0.29 −0.1 −0.29 −0.684 −0.086 0.47 0.03

X 2 X4 0.92 0 0 −0.68 0.03 3.75 × 10−3 9 × 10−4 5.62 × 10−5

X 1 X2 X4 0.99 0.1 0.23 0.104 0.204 0.026 0.0416 2.6 × 10−3

X 3 X4 0.79 0.024 −0.2 −0.4 1.13 0.14 1.28 0.08

X 1 X3 X4 0.86 0.07 0.1 0.23 0.784 0.098 0.615 0.039

X2 X3 X4 0.9 0.07 0.094 0.3 0.63 0.079 0.4 0.025

X1 X2 X3 X4 0.98 0.08 0.01 −0.084 −0.384 −0.048 0.147 9.18 × 10−3

3. Results and analysis region were found to be significant at the α = 0.1 level. At this

stage, it was decided to construct and identify a second-order

3.1. Screening experiment polynomial model.

The data given in Table 2 was used to estimate the main and 3.2. RSM and FCCC design

interaction effects and sum of squares of the factors by using

Yates’ Algorithm as illustrated in Table 4. A second-order polynomial model between significant fac-

To compare the magnitude of the curvature in the studied tors and response was selected to illustrate the dependence of

region, sum of squares of curvature was calculated from Eq. response on the significant factors as given in Eq. (15):

(14). The average values of 3 runs at the center point and 16 fac-

torial points of the design were calculated being 0.788 and 0.586, Y = b0 + b33 X32 + b44 X42 + b3 X3 + b4 X4 + b34 X3 X4 (15)

respectively. Sum of square of curvature was calculated being

0.103 by using Eq. (14). To compare the magnitude of estimated To estimate the model parameters, FCCC design matrix was

factor effects given in Table 4 and curvature with the experimen- constructed as given in Table 3. Since temperature and agitation

tal error, variance analysis was made and given in Table 5. rate were found to be insignificant factors at the end of the

As can be seen from Table 5, main effects of initial concentra- screening phase, 16 screening experiments were considered

tions of NaOH and EtOAc and also the curvature over the studied as a full two-level factorial experimental design for 2 factors

Table 5

Variance analysis of factor effects

Sources of SSeffect d.f. MSSeffect F Critical F-value

variation

X2 0.0115 1 0.0115 1.1

X3 0.1825 1 0.1825 17.38

X4 1.77 1 1.77 168.6

X1 X2 1.10−6 1 1.10−6 9.52 × 10−5

X1 X3 0.02 1 0.02 1.9

X1 X4 0.03 1 0.03 2.85

X2 X3 1.8.10−3 1 1.8 × 10−3 0.17

X2 X4 5.62 × 10−5 1 5.62 × 10−5 5.35 × 10−3

X3 X4 0.08 1 0.08 7.6

X1 X2 X3 2.53 × 10−3 1 2.53 × 10−3 0.24

X1 X2 X4 2.6 × 10−3 1 2.6 × 10−3 0.25

X1 X3 X4 0.039 1 0.039 3.71

X2 X3 X4 0.025 1 0.025 2.38

X1 X2 X3 X4 9.18 × 10−3 1 9.18 × 10−3 0.87

Curvature 0.103 1 0.103 9.8

Error 0.021 2 0.0105

Total 2.37 18

N. Bursali et al. / Chemical Engineering and Processing 45 (2006) 980–989 985

Table 6

Variance analysis of Eq. (16)

Source of SSeffect d.f. MSSeffect F-value Critical F-value

variation

X3 0.24 1 0.24 17.14

X4 2.07 1 2.07 147.86 F0.1(1,18) = 3.007

X32 1.4 × 10−4 1 1.4 × 10−4 0.01

X42 0.1 1 0.1 7.14 F0.1(3,15) = 2.49

X3 X4 0.079 1 0.079 5.64

Residuals 0.25 18 0.014

Lack-of-fit 0.020 3 0.0067 0.45

Pure error 0.23 15 0.015

Total 2.8 23

using least square parameter estimation method, factor effects

were identified as given by Eq. (16):

Y = 0.77 − 0.12X3 + 0.34X4 − 6.6 × 10−3 X32

− 0.18X42 + 0.07X3 X4 (16)

The variance analysis of Eq. (16) was made in Table 6. The

quadratic effect of NaOH and lack-of-fit term were insignificant

at the α = 0.1 significance level. The quadratic effect was

ignored and included in lack-of-fit term. The second-order

model was rearranged as given by Eq. (17):

Y = 0.77 − 0.12X3 + 0.34X4 − 0.18X42 + 0.07X3 X4 (17)

Variance analysis of Eq. (17) was given in Table 7. The

lack-of-fit term was not significant at the α = 0.1 significance

level after moving X32 term and Eq. (17) was found to be

adequate to represent our data with calculated 0.9 R2 value.

The validation of Eq. (17) was checked by using graphical

residual analysis. The residuals were calculated from the fol- Fig. 2. Normal graph of residuals.

lowing equation:

residuals = Yi,obser − Yi,pred (18)

In Fig. 2 normal graph of residuals was given. As can be seen all

residuals lie on a straight line which shows that residuals were

distributed normally. But only one residual deviated from the

straight line.

In Fig. 3, the predicted responses were plotted versus residu-

als to check the assumption that the random errors are distributed

Table 7

Variance analysis of Eq. (17)

Source of SSeffect d.f. MSSeffect F-value Critical F-value

variation

X3 0.24 1 0.24 18.46

X4 2.07 1 2.07 159.2 F0.1(1,19) = 2.99

X42 0.15 1 0.15 11.54

X3 X 4 0.079 1 0.079 6.08 F0.1(4,15) = 2.361

Residuals 0.25 19 0.013

Lack-of-fit 0.020 4 0.005 0.34

Pure error 0.23 15 0.015

Total 2.8 23

Fig. 3. The predicted responses vs. residuals.

986 N. Bursali et al. / Chemical Engineering and Processing 45 (2006) 980–989

Table 8

Variance analysis of Eq. (19)

Source of SSeffect d.f. MSSeffect F-value Critical F-value

variation

X3 0.33 1 0.33 54.1

X4 1.68 1 1.68 275.40 F0.1(1,18) = 3.007

X42 0.12 1 0.12 19.67

X3 X 4 0.14 1 0.14 22.95

Residuals 0.11 18 0.0061

Lack-of-fit 0.023 4 0.0057 0.81

Pure error 0.098 14 0.007

Total 2.5 22

Table 8 it was clear that the lack-of-fit term was not important

after moving outlier data. The standard error associated with

each coefficient was calculated by using Design Expert 6.0.10

Fig. 4. Graph of residuals vs. sodium hydroxide concentration levels.

trial software.

The validation of Eq. (19) was reanalyzed by using residuals.

with mean zero and constant variance. All residuals were dis- The normal graph of residuals, residuals versus predicted values

tributed between −1.6 and +1.6 without having any systematic and factor levels were given in Figs. 6–9, respectively. Since

structure but only one residual was different from the others. the residuals were distributed normally with constant variance,

In Figs. 4 and 5, the graphs of residuals versus NaOH mean zero and independently, it was concluded that Eq. (19) was

and EtOAc concentrations levels were given respectively. From good to fit the experimental data. In other words, the underlying

those figures, an outlier data was determined at minimum levels assumptions about the errors were satisfied. The calculated R2

of both factors. Except that outlier, random errors distributed value for Eq. (19) was 0.95.

independently from the factor levels. At the end of the study, response surface contours were

From the residual graphs, the outlier data was determined obtained by using Eq. (19) at different levels of initial NaOH

being the first experiment in Table 3 and was ignored. At this and EtOAc concentrations and given in Fig. 10. The maxi-

stage the quadratic model parameters were recalculated and mum predicted XA was obtained about 100% at approximately

given by Eq. (19): 0.01 mol L−1 NaOH and 0.1 mol L−1 CH3 COOC2 H5 concen-

trations. The numbers on the corner and edge sides of Fig. 10

Y = 0.77(±0.034) − 0.14(±0.02)X3 + 0.32(±0.02)X4 shows the number of experimental runs that made at these points

as can be seen from Table 3. At the bottom side on the left corner

+ 0.16(±0.039)X42 + 0.096(±0.021)X3 X4 (19)

Fig. 5. The graph of residuals vs. ethyl acetate concentration levels. Fig. 6. Normal graph of residuals of Eq. (19).

N. Bursali et al. / Chemical Engineering and Processing 45 (2006) 980–989 987

Table 9

Results of confirmatory experiments

Number of NaOH concentration EtOAc concentration Experimental Predicted from

experiment (mol L−1 ) (mol L−1 ) Eq. (19)

2 0.07 1 0.91 0.91

3 0.01 1 0.92 0.92

4 0.01 1 0.94 0.92

Fig. 7. Graph of residuals vs. predicted values from Eq. (19). Fig. 9. Graph of residuals vs. ethyl acetate concentration levels.

run at minimum levels of NaOH and EtOAc concentration was

found to be an outlier and removed from the experimental data.

Some experiences are realized to verify the optimum pre-

dicted values by the model. In order to be sure about the fitness

of predicted and observed responses, four confirmatory experi-

ments were made and given in Table 9.

tion process with respect to both operational efforts, consumed

raw materials and obtained yield. As a result of the screen-

ing experiment, temperature and agitation rate were found to

Fig. 8. Graph of residuals vs. sodium hydroxide concentration levels. be insignificant operating parameters whose selected maximum

988 N. Bursali et al. / Chemical Engineering and Processing 45 (2006) 980–989

and minimum ranges were 20–40 ◦ C and 50–250 rpm, respec- process. The maximum predicted conversion rate was calculated

tively in this study. To reach the maximum XA , initial NaOH 0.98 from Eq. (19) at determined optimum condition.

and EtOAc concentration values were determined as 0.01 and On the basis of Eq. (19) and Fig. 10 it was concluded that

0.1 mol L−1 , respectively by using RSM. These experimental absolute value of linear effect of EtOAc was more significant

results were really more reliable and applicable for us to operate than its quadratic effect. The negative quadratic effect of EtOAc

the underlying process under these conditions. was pronounced above 0.055 mol L−1 by indicating the decrease

In this study, two types of experimental design methods in conversion rate with the increasing EtOAc concentration.

were used for screening and response surface identification. The positive linear effect of EtOAc was pronounced below the

Both methods were applied successively, which was one of the 0.055 mol L−1 and causing an increase in conversion rate. The

advantage of the application of statistical experimental design mutual effect of NaOH and EtOAc was found to be the least

technique. Both methods were found to be efficient and easy to significant effect of all the other factor effects. However, its F-

determine important operating parameters, optimum conditions value was found to be 22.95 by indicating a significant effect of

and to interpret the results of experiments and to improve the mutual effect. The mutual effect can be seen in an elliptical shape

process in a short time. At the screening experimentation stage, in proportional with its significance in Fig. 10. The negative first

effects of the factors were determined by using Yates’ Algo- order effect of NaOH was clear especially at higher concentra-

rithm [1,2,10]. Temperature and agitation rate were found to tion of it. Increasing NaOH concentration from 0.01 mol L−1 to

be the insignificant factors and initial NaOH and EtOAc con- the 0.1 mol L−1 decreased the conversion rate.

centrations and their quadratic effects were found to be the In the hydrolysis of esters, the alkali plays a role as a catalyst.

significant factors. At the second phase, process optimization So, it is expected to find that the reaction occurs at very low OH−

was proposed and RSM was applied by using face-centered cen- concentration. In Fig. 10, low NaOH concentration was utilized

tral composite (FCCC) design [1,2]. A second-order polynomial to obtain 0.98 predicted NaOH conversion. This optimal value is

model was identified by using least-square parameter estimation valid between 0.01 and 0.1 mol L−1 NaOH concentration levels.

method. The validation of quadratic model was confirmed by In this study to provide a general confidence and harmony

using graphical residual analysis such as normal graph of resid- in the whole of the statistical analysis, significance level was

uals, graphs of residuals versus predicted values and factors [2]. not changed and selected 0.1 and was determined at the brain

It was concluded that the second-order model was adequate to storming stage of this study by considering used experimental

fit the data. methods, apparatus and examined reaction.

When the objective of an experiment is to make a screen

between the factors, which are less than 5, Full two-level fac- Acknowledgement

torial and fractional factorial experimental designs are recom-

mended. There are three different response surface methods. The authors gratefully acknowledge Ankara University Sci-

These are central composite circumscribed (CCC) design, cen- entific Research Projects for providing financial support (Grant

tral composite inscribed (CCI) design and face-centered central No. 2004 07 45 024).

composite design (FCCC) [2]. In this study, fractional facto-

rial design was not selected since some of the factor effects Appendix A. Nomenclature

could have been confused. FCCC design was chosen, since the

selected minimum levels of factors was not suitable to apply the

other central composite designs. The level selection at the brain- bi regression coefficient

storming stage is really very important, especially in the study C specific conductivity at time t (S)

of process improvement. CEtOAc ethyl acetate concentration (mol L−1 )

Graphical residual analysis was applied in this study to check CNaOH sodium hydroxide concentration at time t (mol L−1 )

the adequacy of the equations and the underlying assumptions, CNaOH,0 sodium hydroxide concentration at time t = 0

to determine the outlier data, to have more reliable and accu- (mol L−1 )

rate results. There are different numerical methods to test the CNaOH,∞ sodium hydroxide concentration at time t = ∞

equation adequacy such as R2 statistic, which is the measure of (mol L−1 )

the variance in the response explained by the model. But these C0 specific conductivity at time t = 0 (S)

numerical methods does not merely guarantee the agreement of C∞ specific conductivity at time t = ∞ (S)

the model with the data as can be seen from our results. In addi- d.f.1 degrees of freedom for effect

tion to numerical methods, graphical residual analysis must be d.f.2 degrees of freedom for error

done. The calculated R2 value was 0.9 before graphical resid- F Fisher’s F-value

ual analysis. With the result of graphical analysis, calculated R2 k second-order rate constant (L mol−1 s−1 )

value was improved. In this study calculated R2 value was 0.95 MSSerror mean sum of square of error

for Eq. (19). This meant that our final equation could explain MSSeffect mean sum of square of effect

the 95% of variation in the response. Our graphical and numer- n replication number

ical results were in agreement with each other. On the basis of nC number of the center point experiment

the confirmatory runs and Table 9, it is noted that Eq. (19) fits nF number of factorial design point

the experimental data and explains the examined saponification N number of experiment

N. Bursali et al. / Chemical Engineering and Processing 45 (2006) 980–989 989

−rNaOH sodium hydroxide consumption rate (mol L−1 s−1 )

SScurvature sum of square of curvature [1] D.C. Montgomery, Design and Analysis of Experiments, 3rd ed., John

Wiley & Sons, New York, 1991, pp. 270–569.

SSerror sum of square of error [2] NIST/SEMATECH e-Handbook of Statistical Methods, 2005.

SSeffect sum of square of effect http://www.itl.nist.gov/div898/handbook/.

Ui,average average value of ith factor [3] J.M. Carr, E.A. McCracken, Statistical program planning for process

Ui,max maximum value of ith factor development, Chem. Eng. Prog. 56 (11) (1960) 56–61.

Ui,min minimum value of ith factor [4] E.E. Lind, J. Goldin, J.B. Hickman, Fitting yield and cost response

surfaces, Chem. Eng. Prog. 56 (11) (1960) 62–68.

Ui,natural natural value of ith factor [5] C.-P. Xu, S.-W. Kim, H.-J. Hwang, J.-W. Yun, Application of statistically

XA fractional conversion rate of sodium hydroxide based experimental designs for the optimization of exo-polysaccharide

Xi codified value of ith factor production by Cordyceps milltaris NG3, Biotechnol. Appl. Biochem. 36

X1 codified value of agitation rate (2002) 127–131.

X2 codified value of temperature [6] M.J. Anderson, H.P. Anderson, Applying DOE to microwave popcorn,

Process Ind. Quality (1993) 30–32.

X3 codified value of initial NaOH concentration [7] S.E. Kruger, I.C. Silva, J.M.A. Rebello, Factorial design of experiments

X4 codified value of initial EtOAc concentration applied to reliability assessment in discontinuity mapping by ultrasound,

ȳC average response at the center point NDT Net 3 (11) (1998).

yC,i ith response at the center point [8] B.V. Mehta, H. Ghulman, R. Gerth, Extrusion die design: a new method-

ȳF average response of the factorial design points ology of using design of experiments as a precursor to neural networks,

JOM-e 51 (9) (1999).

Y process response [9] E.M. Terry, J. Stieglitz, J. Am. Chem. Soc. 49 (1927) 2216–2222.

Yi,obser. ith observation in experimental data [10] D. Cuthbert, Applications of Statistics to Industrial Experimentation,

Yi,pred. ith predicted value of response from fitted model John Wiley & Sons, New York, 1976, pp.17–20, 72–126.

Ui incremental value of ith factor [11] http://www.uni-regensburg.de/Facultaeten/nat Fak IV/Organische-

Chemie/Didaktik/Keusch/cassy est-e.htm.

[12] http://www.statease.com, Minneapolis, USA, 2005.

Greek letters

α significance level

α* star point of FCCC design

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