Development of Electronic Textbook for Chemical Experiment

Taking Esterification as an Example

Akira Ikuo,

Yusuke Yoshinaga and Haruo Ogawa

Department of Chemistry, Tokyo Gakugei University, Tokyo 184-8501, Japan

Keywords: CG, Visualization, Electronic Textbook, Chemical Experiment.

Abstract: Developing policy of electronic textbook for chemical experiment of student’s laboratory at the university

was decided which aimed at integration of observable level experiment and the molecular world. The

developed textbook could display picture of apparatus and flow-chart of small-scale experiment in addition

to CG teaching material. The CG teaching material in the textbook effectively demonstrates images of

dynamical reaction mechanism. Students were able to conduct experiment smoothly and safely with the

electronic textbook inserted in the Ziploc type plastic bag.

1 INTRODUCTION

Understanding the observed phenomena, chemists

use to imagine and explain observations in terms of

molecules. Observed phenomena and molecular

level models are then represented in terms of

mathematics and chemical equation (Gilbert, 2009

and Tasker, 2010). Student’s difficulties and

misconceptions in chemistry are from inadequate or

inaccurate models at the molecular level (Kleinman,

1987). A molecular structure visualized by the

computer graphics (CG) provides a deeper

understanding of molecular structure (Tuvi-Arad,

2006).

It is our aim to produce a CG teaching material

based on quantum chemical calculations, which

provides realizable images of the nature of chemical

reaction (Ikuo, 2006 and 2009). Molecular level

animations combined with video clips of

macroscopic phenomena enabled students to predict

the outcome better (Velazquez-Marcano, 2004). If

the CG teaching material is combined with chemical

experiments of student’s laboratory, students would

observe the reaction from three thinking levels,

namely, phenomena in the actual observable level

and CG teaching material in the molecular level, and

chemical equation in the symbolic level.

The CG teaching material on the tablet computer

was effective to provide image of “Energy” change

and also effective to provide image of “Structure”

change and “Migration of Electron” during chemical

reaction (Ikuo, 2012). Our ultimate goal is to

produce an electronic textbook linking chemical

experiment, which integrates these three levels.

This paper introduces our works of CG

visualization of fundamental chemical reactions for

realizing certain images of the reaction mechanism

and development of the electronic textbook for

chemical experiment of student’s laboratory at the

university, which integrates the observable level

experiment and the molecular world of the

esterification.

2 DEVELOPMENT OF

ELECTRONIC TEXTBOOK

2.1 Policy

Flow chart of development of the electronic

textbook for chemical experiment is shown in the

Scheme 1. Reaction was selected based on

importance in fundamental chemistry. To exhibit

phenomena, experimental condition was optimized

for the student laboratory and experimental program

was made. For easier understanding of experimental

procedure, enlargeable-photos and flow charts were

used in addition to regular text-base description. The

electronic textbook could acts as an individual

electronic tutor. To provide image of molecular

world, computer graphics (CG) images such as

realistic shape of molecules, CG teaching material

(movie) were made based on quantum chemistry

553

Ikuo A., Yoshinaga Y. and Ogawa H..

Development of Electronic Textbook for Chemical Experiment - Taking Esteriﬁcation as an Example.

DOI: 10.5220/0005491705530557

In Proceedings of the 7th International Conference on Computer Supported Education (CSEDU-2015), pages 553-557

ISBN: 978-989-758-108-3

 2015 SCITEPRESS (Science and Technology Publications, Lda.)

calculation. Students would be able to see structure

and energy change during reaction while they are

watching actual reaction progress. In this manner,

observable level experiment and the molecular

world could be integrated. In order to use the

electronic textbook on the lab bench, it need to be

covered with a waterproof, Zip-lock type, case.

Scheme 1: Flow chart of developing method.

2.2 Method

2.2.1 Quantum Chemical Calculation

Structures of intermediates on reactions and their

electrostatic potentials on electron density were

calculated as follows: the semi-empirical molecular

orbital calculation software MOPAC (Stewart, 1989)

with AM1, PM3, and PM5 Hamiltonian in the

CAChe Work System for Windows (Former name of

SCIGRESS, ver. 6.01, FUJITSU, Inc.) was used in

all of calculations for optimization of geometry by

the Eigenvector Following method, for search of

transition state by use of the program with Saddle

point Search, and for search of the reaction path

from the reactants to the products via the transition

state by the intrinsic reaction coordinate (IRC)

calculation (Fukui, 1970). Details of procedure of

the quantum chemical calculations were described in

the previous paper (Ikuo et al., 2006). The

electrostatic potential on electron density (EPED)

(Kahn, 1986) was calculated based on structures

from the results of the IRC calculation.

2.2.2 CG Teaching Material and Electronic

Textbook

A movie of the reaction path was produced by the

software DIRECTOR (ver. 8.5.1J, Macromedia,

Inc.) following the display of the bond order of the

structure of the reactants in each reaction stage,

which was drawn by the CAChe. The obtained CG

of EPED model was combined with those of ball-

and-stick model and reaction profile in the same

reaction stage. It was confirmed that the drawn CGs

of the molecular models of reactants moves

smoothly. The green ball, which indicates progress

of the reaction, was arranged on the reaction profile

and simultaneous movements of the ball and the

reactants were confirmed. Created movie file was

converted to the Quick Time movie for iPad by the

Quick Time PRO (ver. 7.66, Apple, Inc.). Electric

textbook was produced with iBooks Author (ver.

2.1.1, Apple, Inc.) and was saved to iPad (Apple,

Inc.) by using the iTunes (ver. 11.2.1, Apple, Inc.).

3 ELECTRONIC TEXTBOOK

3.1 Contents of Electronic Textbook

3.1.1 Reactions

Formation of HF: The CG teaching material of

rearrangement by collision of diatomic molecule and

F + HCl → HF + Cl

(1)

one atom as shown in equation (1) was developed.

Potential energy (PE) of 2-D and 3-D is shown in

the Figure 1. The figure clearly shows these changes

of PEs with display on PE surface in 3-D, which

offers a bird-eye view of the reaction profile. Two

Valleys of lower energies and hilltop on the

transition state at the saddle point can be recognized

boldly. Possible pathways of the reaction from the

reactants of F and HCl to the products of HF and Cl

via the transition state at saddle point can be readily

traced. The CG teaching material is able to provide

information about change of the PE and structure of

reactants in a certain state simultaneously.

Figure 1: CG teaching material of HF formation.

CSEDU2015-7thInternationalConferenceonComputerSupportedEducation

554

Walden’s inversion: Structural change of reactants

in the reaction, shown in the Scheme 2, was studied

as a model of Walden’s inversion.

Scheme 2: Images of Walden’s inversion.

Reaction of hydroxide and chloromethane is a

typical example of the Nucleophilic Substitution in

the 2

order reaction. Carbon atom at the centre to

which halogen attaches is attacked by the

nucleophile, hydroxide, from a position 180 degrees

from chlorine and then methyl alcohol forms.

Picture of CG movies are shown in the Figure 2. The

CG shows the reaction profile, which demonstrates

the degree of the reaction progress by the ball

indicating the potential energy vs. the reaction

coordinate. Movies were made by using not only the

ball-and-stick model, which shows change in

molecular configuration easily, but also the space-

filling model, which shows realistic shape. A student

is expected to obtain the image of an umbrella

reverse like motion in Walden’s inversion.

Figure 2: CG teaching material of Walden’s inversion.

Nitration of Benzene: A picture of teaching

material is shown in the Figure 3. Left part of the

material shows the reaction profile, potential energy

vs. reaction coordinate, which indicates the degree of

the reaction progress by the red ball on the profile.

Right part shows structural change shown in ball and

stick model, While choreographed animation of

chemical reaction are common (For example, Tasker

& Dalton, 2010), CG based on theory in the present

study could provide not only images of energy

change but also images of dynamical structure

change with more realistic shape.

Figure 3: CG teaching material of benzene nitration.

Esterification of Ethanol and Acetic Acid: The

mechanism of esterification of acetic acid and ethyl

alcohol the reaction is well known (For example

Loudon, 1984), and generally, the esterification

proceeds in the presence of proton catalyst. The rate-

determining step includes the paths of an attack of

the oxygen atom of hydroxyl group of ethyl alcohol

to the central carbon of the formed carbonium ion

and release of water as shown in the Scheme 3. This

step dominates all over the reaction.

Scheme 3: Mechanism of esterification on the rate-

determining step.

Figure 4: CG teaching material of esterification.

The Figure 4 shows the combination CGs on the

way from the state of reactants to that of products

via the transition state. The teaching material

demonstrates the changes of electrostatic potential

and realistic shape of the intermediate of the reaction

on the reaction profile in all stages at the same time.

C Cl

‐

＋

DevelopmentofElectronicTextbookforChemicalExperiment-TakingEsterificationasanExample

555

Distribution of the electrostatic potential among

the intermediate can be seen by the colours. The

model by electrostatic potential provides information

about electrostatic distribution of the intermediate on

the way of the reaction.

3.1.2 Feature of Electronic Textbook

The CG teaching material of the esterification was

combined with chemical experiments of student’s

laboratory for the purpose of making electronic

textbook of basic chemistry to provide experiment at

the observable-level, CG visualization at the

molecular-level, and chemical equation at the

symbolic-level.

The electronic textbook was inserted with images

of experimental procedure in the flow charts and

photographs, which can be enlarged by students

touch (Figure 5). Student can write memo for the

observation. CG teaching materials of reaction

profiles were also inserted (Figure 6). When student

touches the CG teaching material in the tablet

Figure 5: Experimental procedure in electronic textbook.

Figure 6: CG teaching material in electronic textbook.

Figure 7: Electronic textbook with waterproof cover.

computer, the teaching material appears to show

image of the structural change during the reaction.

Student can compare different reaction mechanisms.

If student touches the material again, the Quick

Time control bar appears and the green ball on the

profile can move by student’s choice. Student can

manipulate the reaction back and forth until they

obtain the image of the reaction.

Students were able to conduct experiment smoothly

and safely with the electronic textbook inserted in

the Ziploc type plastic bag (Figure 7).

4 CONCLUSIONS

Developing policy of electronic textbook for

chemical experiment of student’s laboratory at the

university was decided which aimed at integration of

observable level experiment and the molecular

world. The electronic textbook was developed

according to the policy. The developed textbook

could display picture of apparatus and flow-chart of

small-scale experiment in addition to CG teaching

material. The CG teaching material in the textbook

effectively demonstrates images of dynamical

reaction mechanism. From the preliminary study,

students were able to conduct experiment smoothly

and safely with the electronic textbook inserted in

the Ziploc type plastic bag. The developed electronic

textbook could be used to integrate the observable

level experiment and the molecular world.

ACKNOWLEDGEMENTS

This work was supported by JSPS Grant-in-Aid for

Scientific Research (C) (25350188).

CSEDU2015-7thInternationalConferenceonComputerSupportedEducation

556

REFERENCES

Fukui, K., 1970. A Formulation of the Reaction

Coordinate, J. Phys. Chem., 74, 4161-4163.

Gilbert, J. K., Treagust, D. F., 2009. in Gilbert, J. K.,

Treagust, D. (eds.), “Models and Modelling in Science

Education Vol. 4 Multiple Representations in

Chemical Education”, Springer, 333-350.

Ikuo, A., Ikarashi, Y., Shishido, T. and Ogawa, H., 2006.

User-friendly CG visualization with animation of

chemical reaction: esterification of acetic acid and

ethyl alcohol and survey of textbooks of high school

chemistry, Journal of Science Education in Japan, 30

(4), 210-215.

Ikuo A., Nagashima H., Yoshinaga Y., and Ogawa H.,

2009. Calculation of potential energy in the reaction of

“I + H

→ HI + H”, and its visualization, The

Chemical Education Journal (CEJ),

Registration #13-2.

Ikuo, A., Nagashima, H., Yoshinaga, Y., and Ogawa, H.,

2012. Development and practice of teaching material

in tablet computer based on computer graphics by

quantum chemistry calculation - Reaction of I + H

→

HI + H -, Proc. 7th IEEE Intl. Conf. on Wireless,

Mobile, and Ubiquitous Technologies in Educ., 82-86.

Ikuo, A., Yoshinaga, Y., and Ogawa, H., 2014. An

Approach to the Electronic Textbook of Basic

Chemistry Linking Chemical Experiments - CG

Teaching Materials Based on Quantum Chemical

Calculation -, Proc. 5th Intl. Conf. on Computer

Supported Educ. (CSEDU 2013), 688-691.

Ikuo, A., Yoshinaga, Y., and Ogawa, H., 2014. CG

Teaching Material for the Electronic Laboratory

Textbook - Esterification of Acetic Acid and Ethanol,

Proc. 6th Intl. Conf. on Computer Supported Educ.

(CSEDU 2014), 226-231.

Kahn, S. D., Pau, C. F., Overman, L. E. and Hehre, W. J.,

1986. Modeling Chemical Reactivity. 1.

Regioselectivity of Diels-Alder Cycloadditions of

Electron-Rich Dienes with Electron-Deficient

Dienophiles, J. Am. Chem. Soc., 108, 7381-7396.

Kleinman, R. W., Griffin, H. C., Kerner, N. K., 1987. J.

Chem. Edu., 64, 766-770.

Loudon, G. M., 1984. Organic Chemistry, Addison-

Wesley Publishing Co., Inc., p.1010.

Stewart, J. J. P., 1989. Optimization of parameters for

semi empirical methods I. Method, J Comp. Chem., 10

(2), 209–220.

Tasker, R., Dalton, R., 2010. in Gilbert, J. K., Reiner, M.,

Nakhleh, M. (Eds.), “Models and Modelling in

Science Education Vol. 3 Visualization: Theory and

Practice in Science Education”, Springer, 103-131.

Tuvi-Arad, I. and Blonder, R., 2006. Continuous

symmetry and chemistry teachers: learning advanced

chemistry content through novel visualization tools,

Chem. Educ. Res. and Pract., 11(1), 48-58.

Velazquez-Marcano, A., Williamson, V. M., Ashkenazi,

G., Tasker, R. F., and Williamson, K. C., 2004. The

use of video demonstrations and particulate animation

in general chemistry, J. Sci. Educ. and Tech., 13(3),

315-323.

DevelopmentofElectronicTextbookforChemicalExperiment-TakingEsterificationasanExample

557