database on ionic liquids solubilities in molecular ...bulletin.acscinf.org/pdfs/247nm109.pdf ·...

9/19/2014Johan Jacquemin

Database on ionic liquids solubilities

in molecular solvents: progress and

prospects

Johan JACQUEMINQueen’s University Belfast

1

IUPAC Project # 2011-065-3-500

Zdeněk Wagner and Magdalena BendovaInstitute of Chemical Process Fundamentals - Prague


Scope of Presentation

Motivation

Current state of the IUPAC project

Database philosophy, workflow and presentation

Data processing

Example: [C4mim][PF6] + 1-butanol

Conclusions

2


Property database

Data analysis Recommended data

LLE – IL based binary mixtures

3

Motivation


Property database

Establishment / validation of predictive models


4

Motivation


Property database

Relationships between structure and property


5

Motivation


Property database

Web-based interface General public


6

Motivation


Motivation

Ionic Liquids:

Application as task-specific solvents

Structure-property relationships

To critically evaluate existing correlation / prediction models e.g.

UNIFAC, NRTL, COSMO-RS, EoS, etc

Thermodynamic model parameters implementation into e.g. Aspen

Plus.

Why the LLE?

• Organic co-solvents to modify their properties (density,

viscosity, etc)

• Separation processes – azeotrope breaking, CO2 capture,

olefin/paraffin separations

7


Current state of project

Data literature research and database up to 2013

Complete containing more than:

• 60 different ILs structure

• 100 organic solvents

• 300 articles

• 3000 data points

Data literature research and database 2014-now

Under way

Web-based interface ready for data upload

Accessible only to project members

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Database philosophy and Access

A user-friendly interface

Easy data upload

Multistage control of uploaded datasets

XML-based communication language

Interconnectivity of different databases

Easy data export

Access

Administrators – full access

Maintainers - add and edit data

Ordinary users - read-only access to data in the public part

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Database editing

Multistage control of data upload:

Editing

Incomplete table owned by one of the maintainers

Other maintainers may view but cannot edit

Private

Complete table not yet approved by administrator

Any maintainer may start editing

Public

Publicly accessible table by ordinary users

If need be, any maintainer is allowed to edit it

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Workflow


New table started by maintainer

Editing stage

Other maintainers read-only access to check and prevent duplicity

of tables

Maintainer finishes table

Table marked as completed and becomes private

Table approval by administrator

Public table

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Workflow troubleshooting


Bug spotted in private or public table

Any maintainer may revert to editing stage and edit

After completion the table becomes private and requires approval

Table in editing stage for a long time (e.g. due to illness of

a maintainer)

Administrator may force it to private stage

Another maintainer can continue

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Database contents

Relational database with following tables:

1. ILs (formula, name, alias/trivial names, CAS number)

2. Molecular Solvents (formula, name, alias/trivial names,

CAS number)

3. Journals (name, abbreviation, CODEN), CODEN search

at http://cassi.cas.org

4. Authors (name, alias names if known, unique ID for the

database purposes)

5. Citation using information from Tables 3 and 4

6. Measurement methods

7. Data

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Required content

Apart from data:

link to the measurement method,

precisions of measurement of all variables,

purity (contents of water, halides, lithium, etc.),

optional unformatted comment:

• e.g. separate information on the contents of chlorides,

bromides, iodides should be entered rather than summing them

up and reporting them as halides.

Literature reference

DOI whenever available: XML formatted record from CrossRef may

be requested by SW.

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Data storage & search procedure

Relational database should be sufficient

Database should contain only controlled vocabulary

Contents must conform to IUPAC standards for data

publication

Search procedure

Ionic liquid

Solvent

Table of systems

• defined by links to table of ILs and table of solvents

15


Database presentation

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Data presentation

The user interface should offer:

download in several data formats, especially in ThermoML

graphical display

support for critical evaluation using modern robust tools based on

mathematical gnostics:

see http://www.math-gnostics.com

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Mathematical gnostics

Non-statistical tool used to efficiently treat small samples

of strongly uncertain data

Robust regression of data: bi-dimensional (true and

uncertain) contributions

No a priori assumption of error distribution function

Let the data speak for themselves

Outlier detection

Determination of typical data and tolerance intervals

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Data processing

Critical assessment of data

Mathematical gnostics

Recommended data

Data correlation

Modified Flory-Huggins equation

UNIFAC group-contribution parameters (R, Q, aij)

Implementation of requested parameters into Aspen

• NB. Other fitting parameters must be also implemented into

Aspen (e.g. CpIG, Cp, density, viscosity, etc)

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An example of data processing

Binary system x [C4mim][PF6] + (1-x) 1-butanol

See Bendová M., Wagner Z.: Liquid-Liquid Equilibrium in Binary

System [bmim][PF6] + 1-Butanol. J. Chem. Eng. Data 2006, 51(6),

2126–2131.

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Good agreement between

experimental data with the

modified FH equation, except

for the critical region



Binary system x [C4mim][PF6] + (1-x) 1-butanol

See Bendová M., Wagner Z.: Liquid-Liquid Equilibrium in Binary

System [bmim][PF6] + 1-Butanol. J. Chem. Eng. Data 2006, 51(6),

2126–2131.

21

The logarithmic scale: clearer

comparison between the exp.

and calculated values at low

concentrations.

It is evident that there may be

discrepancies in the alcohol-

rich phase.



Binary system [C4mim][PF6] + 1-butanol

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Each homogeneity test shows error distribution for all the data together.

Residuals were weighed with the corresponding estimated concentration

measurement uncertainty in the given phase.

The main part = the normal distribution of errors.



Binary system [C4mim][PF6] + 1-butanol

Data by Maurer et al. IL phase

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Errors in the IL phase are

nonhomogeneous, e.g. the

maximum is shifted towards

negative values.

Correlation of this single

dataset highlights a problem in

the experimental method

(sensibility too low, different IL

batches were used,

measurement were done by

more than one person ?)


Towards a database of databases?

Our database – a „mould“ for all the IUPAC databases

Interconnection of the individual databases?

24


Towards a database of databases?

Our database – a „mould“ for all the IUPAC databases

Interconnection of the individual databases?

25

Massive properties databases

Relationships between structure and properties

Pure ILs Mixtures containing ILs


Conclusions

Progress of the IUPAC Project # 2011-065-3-500

Web-based interface up and running

Complete database of solubility data from 2000 to 2014 by the

end of 2014

Towards a JPCRD publication in 2015

• Critical analysis experimental methods and data sets

• Modified Flory-Huggins equation

• UNIFAC group-contribution parameters (R, Q, aij)

Prospects of the project

Implementation of the database into database of databases?

26


Acknowledgements

From QUB – Belfast – UK

Prof. Chris Hardacre

Prof. David Rooney

From ICPF – Prague – Czech Republic

Dr Magdalena Bendova

Dr Zdeněk Wagner

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IUPAC for funding under project

# 2011-065-3-500

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