Enthalpy and Internal Energy Liquids

Solutions and Vapours Emmerich

Wilhelm
Visit to download the full and correct content document:
https://textbookfull.com/product/enthalpy-and-internal-energy-liquids-solutions-and-va
pours-emmerich-wilhelm/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...

Energy Conservation for IoT Devices Concepts Paradigms

and Solutions Mamta Mittal

https://textbookfull.com/product/energy-conservation-for-iot-
devices-concepts-paradigms-and-solutions-mamta-mittal/

Landau Fermi Liquids and Beyond First Edition Tripathi

https://textbookfull.com/product/landau-fermi-liquids-and-beyond-
first-edition-tripathi/

Qigong for Internal Growth Eight Brocades and other

exercises to develop your Energy Robert Downey

https://textbookfull.com/product/qigong-for-internal-growth-
eight-brocades-and-other-exercises-to-develop-your-energy-robert-
downey/

Application, Purification, and Recovery of Ionic

Liquids 1st Edition Olga Kuzmina

https://textbookfull.com/product/application-purification-and-
recovery-of-ionic-liquids-1st-edition-olga-kuzmina/
Novel Catalytic and Separation Processes Based on Ionic
Liquids Dickson Ozokwelu

https://textbookfull.com/product/novel-catalytic-and-separation-
processes-based-on-ionic-liquids-dickson-ozokwelu/

Energy Solutions to Combat Global Warming 1st Edition

Xinrong Zhang

https://textbookfull.com/product/energy-solutions-to-combat-
global-warming-1st-edition-xinrong-zhang/

Low Head Hydropower for Local Energy Solutions 1st

Edition Narrain

https://textbookfull.com/product/low-head-hydropower-for-local-
energy-solutions-1st-edition-narrain/

Lonic liquids in lipid processing and analysis :

opportunities and challenges 1st Edition Cheong

https://textbookfull.com/product/lonic-liquids-in-lipid-
processing-and-analysis-opportunities-and-challenges-1st-edition-
cheong/

Climate Change and Energy Dynamics in the Middle East

Modeling and Simulation Based Solutions Hassan Qudrat-
Ullah

https://textbookfull.com/product/climate-change-and-energy-
dynamics-in-the-middle-east-modeling-and-simulation-based-
solutions-hassan-qudrat-ullah/
 .
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP001

Liquids, Solutions and Vapours

Enthalpy and Internal Energy
 .
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP001 View Online
 View Online

Enthalpy and Internal Energy

Liquids, Solutions and Vapours
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP001

Edited by

Emmerich Wilhelm
University of Vienna, Austria
Email: Emmerich.Wilhelm@univie.ac.at

and

Trevor M. Letcher
University of KwaZulu-Natal, South Africa
Email: trevor@letcher.eclipse.co.uk
.
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP001 View Online

Print ISBN: 978-1-78262-711-1

PDF eISBN: 978-1-78801-021-4
EPUB eISBN: 978-1-78801-196-9

A catalogue record for this book is available from the British Library

r The Royal Society of Chemistry 2018

All rights reserved

Apart from fair dealing for the purposes of research for non-commercial purposes or for
private study, criticism or review, as permitted under the Copyright, Designs and Patents
Act 1988 and the Copyright and Related Rights Regulations 2003, this publication may not
be reproduced, stored or transmitted, in any form or by any means, without the prior
.

permission in writing of The Royal Society of Chemistry or the copyright owner, or in the
case of reproduction in accordance with the terms of licences issued by the Copyright
Licensing Agency in the UK, or in accordance with the terms of the licences issued by
the appropriate Reproduction Rights Organization outside the UK. Enquiries concerning
reproduction outside the terms stated here should be sent to The Royal Society of
Chemistry at the address printed on this page.

Whilst this material has been produced with all due care, The Royal Society of Chemistry
cannot be held responsible or liable for its accuracy and completeness, nor for any
consequences arising from any errors or the use of the information contained in this
publication. The publication of advertisements does not constitute any endorsement by
The Royal Society of Chemistry or Authors of any products advertised. The views and
opinions advanced by contributors do not necessarily reflect those of The Royal Society
of Chemistry which shall not be liable for any resulting loss or damage arising as a result
of reliance upon this material.

The Royal Society of Chemistry is a charity, registered in England and Wales,

Number 207890, and a company incorporated in England by Royal Charter
(Registered No. RC000524), registered office: Burlington House, Piccadilly,
London W1J 0BA, UK, Telephone: þ44 (0) 207 4378 6556.

Visit our website at www.rsc.org/books

Printed in the United Kingdom by CPI Group (UK) Ltd, Croydon, CR0 4YY, UK
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP005

Foreword

I am delighted to write this Foreword in my capacity as Chair of the Inter-

national Association of Chemical Thermodynamics. As a former editor of the
Journal of Chemical Thermodynamics and a long-time researcher and
author in the field of thermodynamics, I see this book as an important
waypoint on our collective journey towards a more complete quantitative
understanding of the thermodynamic properties of matter.
Classical thermodynamics is of course a science of great beauty. Although
founded upon just a few simple laws, it has outstandingly-broad applic-
ability and it underpins much of the physical and life sciences and also finds
widespread application in engineering. From a theoretical point of view,
those few laws, and all that can be formally deduced from them, are well
established. However, quantification of the properties that thermodynamic
theory interrelates remains a vibrant and engaging challenge to be
.

addressed by means of both experimental measurements and the appli-

cation of molecular theory. This book is about two of the most fundamental
of all thermodynamic quantities: enthalpy and internal energy; specifically
the enthalpy and internal energy of fluids. It is of course the case that neither
of these quantities can be measured on an absolute scale, and so it is
changes in enthalpy and internal energy that belong to the currency of
chemical thermodynamics. Like other thermodynamic properties, our
knowledge of enthalpy and internal energy changes rests to a great extent
upon precise experimental measurements and their interpretation according
to both the laws of classical thermodynamics and the predictions of mo-
lecular theory. Calorimeters of various types are the principal means of
carrying out such experiments, and the design of both the instruments
themselves and the experiments carried out in them are key to achieving
meaningful results. Valuable as they are, precise experimental measure-
ments are usually painfully slow to carry out so that the demand for

Enthalpy and Internal Energy: Liquids, Solutions and Vapours

Edited by Emmerich Wilhelm and Trevor M. Letcher
r The Royal Society of Chemistry 2018
Published by the Royal Society of Chemistry, www.rsc.org

v
 View Online

vi Foreword

experimental data usually outstrips supply. Fortunately, statistical mechanics

and molecular theory can greatly amplify the value of experimental meas-
urements by providing a means of predicting thermodynamic properties for
whole classes of substances based on parameters determined from just a few
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP005

well studied systems. The present volume presents the state of the art in both
the experimental and some theoretical aspects of enthalpy and internal energy
changes in fluid systems. Editors Trevor Letcher and Emmerich Wilhelm are
to be congratulated on recruiting a cadre of world-leading specialist authors
who, in 23 chapters, illuminate key aspects of the subject in a modern,
engaging and yet fundamental way. The book brings the subject beautifully up
to date, for example by detailing major advances made in different branches
of calorimetry in recent decades.
The International Association of Chemical Thermodynamics (IACT) was
established to continue the work of the former International Union of Pure
and Applied Chemistry (IUPAC) Commission on Chemical Thermodynamics
in its tasks of:

 Establishing the highest standards in thermodynamics research and in

thermodynamic property measurements
 Promoting the critical compilation, dissemination and application of
thermodynamic data
 Advancing the theoretical understanding of such properties

The importance of this work has been recognised by IUPAC which, at its
General Assembly in Ottawa in 2003, accorded IACT Associated Organisation
.

status. A major role of IACT is the holding of a biennial scientific Confer-

ence, at which the Rossini Lectureship Award and Junior Award are
presented for excellence in chemical thermodynamics. IACT also encourages
joint scientific projects, especially related to data compilations, and pro-
motes the publication of books on chemical thermodynamics. It is within
this latter context, that IACT is delighted to endorse this excellent book.

J. P. Martin Trusler
Imperial College London, U.K.
International Association of Chemical Thermodynamics
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP007

Preface

The majority of chemical processes takes place in fluid systems, hence

properties of gases, vapours and liquids, pure and mixed, are of prime
scientific as well as engineering importance. In fact, many of the significant
developments in physical chemistry, biophysical chemistry, geochemistry
and chemical engineering have originating from chemical thermodynamics as
applied to fluid systems.1–3 However, the most profitable approach for both
applications and theoretical advances is based on the combination of
chemical thermodynamics with molecular theory and statistical mechanics4,5
as a means for or as an aid to the calculation of thermodynamic properties6
(the term molecular thermodynamics was coined by Prausnitz more than forty
years ago). During the last decades, the impressive growth of this field has
been stimulated by the steadily increasing need for thermodynamic property
data and phase equilibrium data in the applied sciences, and has profited
.

greatly by advances in experimental techniques, by advances in the theory of

fluids in general, and by advances in computer simulations of reasonably
realistic model systems.
Internal energy and enthalpy belong to the most important thermo-
dynamic/thermophysical properties, and have played a central role in the
development of formal thermodynamics, i.e. in the formulation of the first
law of thermodynamics,7 introduced as a generalisation and abstraction of
experimental results concerning energy conservation. Measurements of
changes of these properties using calorimeters established one of the oldest
fields of physical chemistry – calorimetry.8,9 In fact, calorimetric determin-
ations of molar enthalpies of mixing/molar excess enthalpies HE belong to the
earliest methods yielding quantitative measures of deviations from ideal-
solution behaviour, and HE data play a pivotal role in equation-of-state
research, which is intimately connected with applied statistical mechanics.
Excess enthalpies provide information complementary to that associated with

Enthalpy and Internal Energy: Liquids, Solutions and Vapours

Edited by Emmerich Wilhelm and Trevor M. Letcher
r The Royal Society of Chemistry 2018
Published by the Royal Society of Chemistry, www.rsc.org

vii
 View Online

viii Preface
E
the excess molar Gibbs energy G which is obtained from measurements of
vapour–liquid equilibria,10 that is to say,
 
@ðGE ðT; P; fxi gÞ=RTÞ H E ðT; P; fxi gÞ
¼ :
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP007

@T P;fxi g RT 2

Here, the temperature is denoted by T, P is the pressure, and {xi} is the set
of compositional variables (mole fractions) characterising the (multi-
component) mixture. Modern flow calorimeters allow reliable measure-
ments of excess enthalpies over extended temperature ranges and at elevated
pressures,11 and the results have to be consistent with heat capacity meas-
urements,12 i.e.,
 E 
@H ðT; P; fxi gÞ
¼ CPE ðT; P; fxi gÞ;
@T P;fxi g

and with volumetric data,13 i.e.,

 E   E 
@H ðT; P; fxi gÞ @V ðT; P; fxi gÞ
¼ V E ðT; P; fxi gÞ  T :
@P T;fxi g @T P;fxi g

Here, CEP denotes the excess molar heat capacity at constant pressure, and VE
is the excess molar volume. Vibrating-tube densimetry,14 in particular, is
well suited for this purpose.
.

This book, entitled Enthalpies and Internal Energies: Liquids, Solutions and
Vapours, is published under the auspices of the International Association of
Chemical Thermodynamics (IACT) and is the third volume in our series
published by the Royal Society of Chemistry, Cambridge, UK; the previous
two, published, respectively, in 2010 and 2015 are:

Heat Capacities: Liquids, Solutions and Vapours, edited by Emmerich

Wilhelm and Trevor M Letcher,12

and

Volume Properties: Liquids, Solutions and Vapours, edited by Emmerich

Wilhelm and Trevor M Letcher.13

Our three books follow a long tradition of publishing reviews of important

areas/topics of current interest in chemical thermodynamics, that started in
1956 with Experimental Thermochemistry, Volume 1 (Interscience Publishers,
Inc., New York, USA), edited by F. D. Rossini (see details in the preface to
Volume Properties13). As done previously, we have looked to the world-wide
international field of thermodynamics for our authors, and in true IACT
spirit our new book has contributing authors from 14 countries: Austria,
 View Online

Preface ix

Belgium, China, France, Germany, Greece, Israel, Japan, Mexico, South

Africa, Spain, Switzerland, United Kingdom and the United States of
America.
The main objectives of our book are as follows. First and foremost, the
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP007

book presents reviews and surveys which are of particular value for re-
searchers wanting to stay informed on recent developments, for researchers
expanding their area of interest and/or are entering a new field, and for those
who desire to understand the origins and the background of a scientific area
and endeavour to see where it is leading to. Many of the topics discussed in
this new volume have not been reviewed before as they have only recently
been researched, or have only recently attracted renewed interest. The re-
views published here include copious references to the literature including
the latest relevant publications (up to mid 2016). Another objective is to
bring together research from disparate disciplines, either from academia or
from the applied sciences, which has a bearing on enthalpy, internal energy
and related properties. Of particular note are the expanding activities
in biophysical chemistry aimed at broadening our understanding of the
thermodynamic basis of physicochemical phenomena associated with bio-
logical processes in living organisms. This book thus provides an overview
and various highlights of a huge field, and we strongly believe that cross-
linking chapters will yield synergistic effects, leading to new ways of looking
at problems in physics, chemistry and chemical engineering, and expanding
the horizons to which solutions can be applied. The book’s success
ultimately rests with the authors and we, the editors, would like to thank all
of them for their cooperation and enthusiastic contributions which are
.

highly valued. Finally, we reiterate (with passion) our philosophy that a

book, be it in electronic or printed form, is the most important vehicle for
disseminating knowledge.
Where possible, the units, symbols and names of thermodynamic quan-
tities have been checked against the rules laid down in the Green Book of the
International Union of Pure and Applied Chemistry.15 In almost all cases the
authors have adhered to the suggestions of IUPAC, and deviations are solely
due to the desire to present a concise, unequivocal and logically consistent
notation in compliance with usage preferred by the scientific community
interested in this book’s topics, i.e. by physical chemists, physicists,
geophysicists, biophysicists and chemical engineers. Such an approach is in
accord with the spirit of the Green Book expressed in the Introduction on
p. XII, i.e., with the principle of ‘‘good practice of scientific language’’. Finally,
we wish to thank the Royal Society of Chemistry, whose representatives were
most helpful and patient in producing Enthalpy and Internal Energy: Liquids,
Solutions and Vapours.
Emmerich Wilhelm
University of Wien, Austria

Trevor M. Letcher
University of KwaZulu-Natal, South Africa
 View Online

x Preface

References
1. J. H. Hildebrand, J. M. Prausnitz and R. L. Scott, Regular and Related
Solutions, The Solubility of Gases, Liquids, and Solids, Van Nostrand
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP007

Reinhold Company, New York, USA, 1970.

2. J. S. Rowlinson and F. L. Swinton, Liquids and Liquid Mixtures,
Butterworth Scientific, London, UK, 3rd edn, 1982.
3. J. M. Prausnitz, R. N. Lichtenthaler and E. G. de Azevedo, Molecular
Thermodynamics of Fluid-Phase Equilibria, Prentice Hall PTR, Upper
Saddle River, New Jersey, USA, 3rd edn, 1999.
4. (a) C. G. Gray and K. E. Gubbins, Theory of Molecular Fluids,
Fundamentals, Clarendon Press, Oxford, UK, 1984, vol. 1; (b) C. G. Gray,
K. E. Gubbins and C. G. Joslin, Theory of Molecular Fluids, Applications,
Oxford University Press, Oxford, UK, vol. 2, 2011.
5. K. Lucas, Molecular Models for Fluids, Cambridge University Press,
New York, USA, 2007.
6. Applied Thermodynamics of Fluids, ed. A. R. H. Goodwin, J. V. Sengers and
C. J. Peters, The Royal Society of Chemistry/IUPAC & IACT, Cambridge,
UK, 2010.
7. J. Kestin, A Course in Thermodynamics, Hemisphere Publishing
Corporation, Washington, USA, revised printing, 1979, vol. I & II.
8. Solution Calorimetry: Experimental Thermodynamics, ed. K. N. Marsh
and P. A. G. O’Hare, Blackwell Scientific Publications/IUPAC, Oxford,
UK, 1994, vol. IV.
9. S. M. Sarge, G. W. H. Höhne and W. Hemminger, Calorimetry:
.

Fundamentals, Instrumentation, and Applications, Wiley-VCH, Weinheim,

Germany, 2014.
10. Dortmund Data Bank Software and Separation Technology: http://
www.ddbst.de.
11. J. B. Ott and C. J. Wormald, Excess Enthalpy by Flow Calorimetry, in
Solution Calorimetry: Experimental Thermodynamics, ed. K. N. Marsh and
P. A. G. O’Hare, Blackwell Scientific Publications/IUPAC, Oxford, UK,
1994, ch. 8, vol. IV, pp. 161–194.
12. Heat Capacities: Liquids, Solutions and Vapours, ed. E. Wilhelm and
T. M. Letcher, The Royal Society of Chemistry/IUPAC & IACT,
Cambridge, UK, 2010.
13. Volume Properties: Liquids, Solutions and Vapours, ed. E. Wilhelm and
T. M. Letcher, The Royal Society of Chemistry/IUPAC & IACT,
Cambridge, UK, 2015.
14. E. Wilhelm and J.-P. E. Grolier, Excess Volumes of Liquid Nonelectrolyte
Mixtures, in Volume Properties: Liquids, Solutions and Vapours, ed.
E. Wilhelm and T. Letcher, The Royal Society of Chemistry/IUPAC &
IACT, Cambridge, UK, 2015, ch. 7, pp. 163–245.
15. International Union of Pure and Applied Chemistry, Quantities, Units
and Symbols in Physical Chemistry, RSC Publishing/IUPAC, Cambridge,
UK, 3rd edn, 2007.
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP011

Contents

Chapter 1 Internal Energy and Enthalpy: Introduction, Concepts and

Selected Applications 1
Emmerich Wilhelm

1.1 Introduction 1
1.2 Thermodynamic Fundamentals 3
1.3 More Thermodynamics and Selected
Applications 14
1.3.1 Properties of Real Fluids 14
1.3.2 Property Changes of Mixing 41
1.4 Concluding Remarks, Outlook and
Acknowledgements 51
References 53
.

Chapter 2 Macroscopic Energy and Entropy Balances in Phase

Equilibrium Studies 62
J. David Raal and Deresh Ramjugernath

2.1 Introduction 62
2.2 Derivation of Macroscopic Balances 63
2.3 Equations 63
2.3.1 Macroscopic Energy Balance 63
2.3.2 Macroscopic Mechanical Energy Balance 64
2.3.3 Macroscopic Entropy Balance 64
2.4 Application of Macroscopic Balances 64
2.4.1 Differential Ebulliometry 64
2.5 Macroscopic Balances in Flow Calorimetry 71

Enthalpy and Internal Energy: Liquids, Solutions and Vapours

Edited by Emmerich Wilhelm and Trevor M. Letcher
r The Royal Society of Chemistry 2018
Published by the Royal Society of Chemistry, www.rsc.org

xi
 View Online

xii Contents

2.6 Some Useful Derivative Relations 73

2.6.1 Limiting Activity Coefficients 73
2.6.2 Temperature and Pressure Derivatives 74
References 76
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP011

Chapter 3 Enthalpy Measurements of Condensed Matter by

Peltier-element-based Adiabatic Scanning
Calorimetry (pASC) 77
Jan Thoen, Jan Leys, Patricia Losada-Pérez and
Christ Glorieux

3.1 Introduction 77
3.2 Operational Principle of Adiabatic Scanning
Calorimetry 78
3.3 Peltier-element-based Adiabatic Scanning
Calorimeter (pASC) 79
3.4 Comparison with DSC 82
3.5 The pASC as Adiabatic Heat-step Calorimeter 83
3.6 The pASC as Heat-flux DSC-type Constant-rate
Calorimeter 84
3.7 The pASC as Power-compensated DSC-type
Constant-rate Calorimeter 84
3.8 High-resolution pASC Data near the Melting Point
of Gallium 85
.

3.8.1 pASC Constant Power Scanning Results 85

3.8.2 pASC Heat-step Results 86
3.8.3 pASC Heat-flux and Power-compensated
DSC-type Scanning Results 87
3.9 High-resolution pASC Data near Phase Transitions
in Lipid Vesicles 89
3.10 High-resolution pASC Data for the Melting of
Water 89
3.11 High-resolution pASC Data for Phase Transitions
in a Liquid Crystal 92
References 94

Chapter 4 Isothermal Titration Calorimetry 96

José Manuel del Rı́o and Jean-Pierre E. Grolier

4.1 Introduction 96
4.2 Thermodynamic Models of the Titration Processes
in Isothermal Titration Calorimetry 102
4.2.1 The Process of Titration in the Different
Types of Titration Cells 102
 View Online

Contents xiii

4.2.2 Run Types in Isothermal Titration

Calorimetry 107
4.2.3 Finite Titrations 112
4.2.4 Infinitesimal Titrations 116
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP011

4.3 Interaction of Solutes in Dilute Solutions by

Isothermal Titration Calorimetry 121
4.3.1 Study of the Single Ligand Binding Site
Model 122
Acknowledgements 129
References 129

Chapter 5 Calorimetric Determination of Enthalpies of Vaporization 133

Dzmitry H. Zaitsau and Eugene Paulechka

5.1 Introduction 133

5.2 Theoretical Considerations 134
5.3 Calorimetric Determination of the Enthalpy of
Vaporization 136
5.3.1 Condensation Apparatuses 137
5.3.2 Vaporization Calorimetry 141
5.3.3 Differential Scanning Calorimetry 154
5.3.4 Fast Scanning Calorimeter (FSC) 155
5.4 Conclusions 156
References 156
.

Chapter 6 Energetic Effects in Hydrogen-bonded Liquids and

Solutions 159
Claudio A. Cerdeiriña, Kateřina Zemánková and
Miguel Costas

6.1 Introduction 159

6.2 Pure Associated Liquids 162
6.2.1 Partitioning of the Heat Capacity of Liquids 162
6.2.2 Two-state Association Model 163
6.3 Nonaqueous Associated Solutions 165
6.3.1 Two-state Behaviour for the Excess Heat
Capacity 165
6.3.2 Inert Solvents versus Proton Acceptors 166
6.4 Cold Water 168
6.4.1 Anomalous Thermodynamics 168
6.4.2 Two-state Analysis 169
6.5 Hydrophobicity 170
6.5.1 Hydration Phenomena 170
6.5.2 Aggregation of Small Amphiphiles 171
 View Online

xiv Contents

6.6 Final Remarks 174

Acknowledgements 175
References 175
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP011

Chapter 7 Thermodynamic Studies of Inclusion Compounds of

Cyclodextrin 179
Takayoshi Kimura

7.1 Introduction 179

7.2 Methods of Determination 180
7.2.1 Experimental 180
7.2.2 Theoretical 181
7.2.3 Quantum Chemical Approach 183
7.3 Thermodynamic Parameters 183
7.3.1 Enthalpy of Dilution 183
7.3.2 Effect of Aliphatic Group Size on a-CD
Inclusion Compounds 184
7.3.3 Positional Effect of Hydroxyl Groups in
Butanediol Isomers 196
7.3.4 Effect of Guest Molecule Functional Groups
on Inclusion into a-CD 199
7.4 Discussion 202
7.4.1 Entropy–Enthalpy Compensation 205
7.5 Closing Remarks 206
.

References 206

Chapter 8 Thermodynamic Studies of Chiral Compounds 212

Takayoshi Kimura

8.1 Introduction 212

8.2 Material and Method 214
8.2.1 Material 214
8.2.2 Calorimetry 214
8.2.3 Theoretical Application 215
8.3 Enthalpic Behaviour 217
8.3.1 Enthalpies of Mixing for Pure Enantiomers
in the Liquid State 217
8.3.2 Interaction of Enantiomers in the Solution
State 222
8.4 Theoretical Comparison 237
8.4.1 Solution Theory: Intermolecular Interaction
of Enantiomers 239
 View Online

Contents xv

8.4.2 Quantum Chemical Calculation 241

8.4.3 Molecular Dynamics Calculation 242
8.5 Closing Remarks 243
References 243
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP011

Chapter 9 Temperature Dependence of the Enthalpy of

Alkanes and Related Phase Change Materials (PCMs) 246
Jan Leys, Patricia Losada-Pérez, Christ Glorieux and
Jan Thoen

9.1 Introduction 246

9.2 Experimental Details 248
9.3 Pure Alkanes and Rotator Phases 248
9.3.1 Background 248
9.3.2 Phase Transitions 250
9.3.3 Overview 251
9.3.4 RI–RII Transition 252
9.3.5 RV–RI Transition 255
9.3.6 Other Transitions 255
9.4 PCMs and Stored Heat 256
9.4.1 Background 256
9.4.2 PCMs 257
9.4.3 Alkane Mixtures 258
.

9.4.4 Fatty Acids 259

9.4.5 Water and Water–Salt Eutectics 259
9.4.6 Composites and Encapsulation 260
9.5 Summary and Conclusion 266
References 266

Chapter 10 Enthalpy Changes on Solution of Gases

in Liquids 269
Emmerich Wilhelm and Rubin Battino

10.1 Introduction 269

10.2 Thermodynamics 270
10.2.1 Gas Solubility 270
10.2.2 Calorimetry 281
10.3 Selected Results 291
10.4 Concluding Remarks 293
References 294
 View Online

xvi Contents

Chapter 11 Titration Calorimetry and Differential Scanning

Calorimetry of Lipid–Protein Interactions 299
Joachim Seelig
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP011

11.1 Introduction 299

11.2 Isothermal Titration Calorimetry 300
11.2.1 Binding of Apolipoprotein A-1 (Apo A-1) to
Lipid Vesicles 300
11.2.2 Langmuir Multi-site Binding Isotherm 303
11.2.3 LAH4-L1-into-lipid Isothermal Titration
Calorimetry 304
11.2.4 Surface Partition Equilibrium and
Gouy–Chapman Theory 306
11.3 Differential Scanning Calorimetry of Lipid–Protein
Interactions 308
11.3.1 Thermal Unfolding of Apo A-1 in Solution
and in Membranes 308
11.3.2 The 2-state Model Applied to Apo A-1 310
11.3.3 Zimm–Bragg Theory 311
11.3.4 Analysis of Calorimetric Protein Unfolding
Experiments 312
References 313
.

Chapter 12 Biocalorimetry: Differential Scanning Calorimetry of

Protein Solutions 315
Pedro L. Mateo, Francisco Conejero-Lara, Irene Luque,
Javier Ruiz-Sanz, Jose C. Martinez, Ana I. Azuaga and
Eva S. Cobos

12.1 Introduction 315

12.2 The Two-state Unfolding Model for Monomeric
Proteins 318
12.3 The Three-state and Multi-state Unfolding Models
for Monomeric Proteins 321
12.4 The Study of Protein–ligand and Protein–Protein
Interactions by DSC 322
12.5 DSC Analysis of Protein Oligomers and
Aggregates 325
12.6 Non-equilibrium Transitions 328
12.7 Conclusions 331
References 331
 View Online

Contents xvii

Chapter 13 Biocalorimetry of Plants, Insects and Soil Microorganisms 336

Lee D. Hansen, Amaia Nogales, Birgit Arnholdt-Schmitt,
Lisa G. Neven and Nieves Barros
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-FP011

13.1 Introduction 336

13.2 Biocalorimetry of Plants 340
13.3 Biocalorimetry of Insects 345
13.3.1 Cold Hardiness 350
13.3.2 Whole Body Supercooling Points 350
13.3.3 Assessment of Pesticide Activity 351
13.3.4 Development of Postharvest Quarantine
Treatments 351
13.4 Biocalorimetry of Soil Organic Matter 353
References 358

Chapter 14 Temperature Dependence of the Enthalpy Near Critical

and Tricritical Second-order and Weakly First-order Phase
Transitions 364
Patricia Losada-Pérez, Jan Leys, George Cordoyiannis,
Christ Glorieux and Jan Thoen

14.1 Introduction 364

14.2 Temperature Dependence of the Enthalpy at the
.

Liquid–Liquid Critical Point 366

14.3 Enthalpy Temperature Dependence at Weakly
First-order and Tricritical Second-order Phase
Transitions 369
14.3.1 Enthalpy Temperature Dependence at the
Weakly First-order Isotropic to Nematic
Transition 370
14.3.2 Enthalpy Temperature Dependence at the
Nematic to Smectic A Phase Transition 371
References 378

Chapter 15 Yang–Yang Critical Anomaly 380

Ilmutdin M. Abdulagatov, Joseph W. Magee,
Nikolai G. Polikhronidi and Rabiyat G. Batyrova

15.1 Background 380

15.2 Isochoric Heat Capacity and Liquid–Gas
Asymmetry 384
 View Online

Internal Energy and Enthalpy: Introduction, Concepts and Selected Applications 7

amount of substance n, and the proportionality factor is known as a specific

property or as a molar property, respectively. Thus, for the extensive total
internal energy we have
U t ¼ mu, (1.15)
Published on 01 September 2017 on http://pubs.rsc.org | doi:10.1039/9781788010214-00001

where u denotes the specific internal energy, an intensive property, or

alternatively we have
U t ¼ nU, (1.16)
where U denotes the intensive molar internal energy. Evidently, the quotient
of any two extensive properties is an intensive property. Hence an extensive
property is transformed into an intensive specific property by dividing by the
total mass, and into an intensive molar property by dividing by the total
amount of substance; a density is obtained when dividing by the total volume
V t ¼ nV. (1.17)
As pointed out, classical thermodynamics is concerned with macroscopic
properties and with relations among them. No assumptions are made about
the microscopic, molecular structure, nor does it reveal any molecular
mechanism. In fact, essential parts of thermodynamics were developed
before the internal structure of matter was established, and a logically
consistent theory can be developed without assuming the existence of
molecules. However, since we do have reliable theories involving molecular
properties and interactions, using appropriate molecule-based models
statistical mechanics allows the calculation of macroscopic properties.
.

Essentially because of this connection, molar properties are used together

with the appropriate composition variable, the mole fraction xi of component
i of a homogeneous system, i.e., of a phase:
,
X
xi  ni ni ¼ ni =n; (1:18)
i
P
where n ¼ ni is the total amount of substance in the phase, and ni is the
i P
amount of component i; xi ¼ 1, and for a pure fluid xi ¼ 1. Of course, use is
i
limited to systems of known molecular composition. Thus, if M t is taken to
represent an extensive total property, such as U t, of a homogeneous system,
the corresponding intensive molar property M is defined by
M  M t/n. (1.19)
The overall molar property of a closed multiphase system, with p equilibrium
phases a, b, . . ., is
,
na M a þ nb M b þ    X p p X p
M¼ ¼ n M n : (1:20)
nt p p
Another random document with
no related content on Scribd:
 Mutta niinkauvan, kun hän jaksoi istua, sai rohdin kuontalokin
kulkea hänen koukistuneitten sormiensa läpi rullalle ja sitä tietä ne
menivät pappilan ruustinnan karvamattolangatkin. —

Pahemmin ei voinut kukaan loukata Miinaa, kun puhumalla

hänelle vaivaishoidon avusta. —

"Häpeäisit!" sanoi hän vihaisesti.

"Ota itse, jos haluat, — mie ennen vaikka kuolen…"

Ja niin kai hän olisi tehnytkin, säästöjensä loputtua, jos ei

tyttärensä olisi saanut häntä houkutelluksi luokseen, nähdessään
että vanhuksen oli mahdoton tulla toimeen yksinäisessä
tupasessaan.

Mutta ei hän sieltä sittenkään aivan mielisuosiolla lähtenyt. —

Pettymyksiä.

Kaarlo heitti pallon huimaavan korkealle ilmaan.

Suuren lapsijoukon käsivarret kohosivat kuin jännitetyt jouset, ne

tempoilivat ja värähtelivät malttamattomuudesta sillä itsekukin oli
mielestään juuri se, jonka käsiin pallon oli määrä pudota… Ja
huudot: minä, minä, minä, raikuivat kilvan puutarhan nurmikolla!

Pojat, jotka luonto on varustanut vahvemmilla käsivarsilla,

rynnistivät etualalle, työntäen kilpailussa heikommat tytöt syrjään.
Mutta yksi niistä — pienin ehkä — vilkas ja vikkelä kuin orava,
pujottausi vikkelästi joukon läpi, ennätti edelle ja ojensi itsepäisesti
pienet, valkoisen pitsin verhoamat käsivartensa ylös, kohti putoavaa
palloa, joka kiisi kuin nuoli suoraan ja empimättä pieniin, pehmoisiin
tytön käsiin.

"Minä!" kajahti riemuhuuto lapsen suusta ja ylpeänä voitostaan

keikautti hän valkohiuksista päätänsä.

Pojat katselivat vähän nyrpeissään sivu suun mennyttä voittoa ja

sieltä täältä kuului ääniä, jotka sanoivat:

"Eihän se Elli olisi voittanut, jos —"

"Eikähän se Elli oikeastaan olisi saanut —" mutta lauseitten

loppuosat haipuivat jostakin syystä niin hiljaisiksi että ainoastaan
vierustoveri saattoi kuulla ne.

Vaan kun Ellin suurien silmien voitonriemu kävi aivan

sietämättömäksi, sanoi suurin pojista kuuluvammalla äänellä: "Eikä
tämä peli oikeastaan tytöille ollutkaan!"

Kun pallopeli alkoi ikävystyttää, heittäytyivät tytöt piiritanssiin

pihamaalle ja pojat lähtivät kiipeilemään leveitä tikapuita ylös
rakennuksen katolle.

"Hei vaan, kuinka kauvas täällä näkee!" huusi kehoittavasti se,

joka ensinnä perille ehti ja sen kuultuaan nekin jotka vielä tikapuitten
juurella seisoivat kapusivat kilvassa ylös. "Ai ihmettä!" kuului
reippaasti ylhäältä.

"Kuinka kaunista!" — "Kuinka hauskaa!" — "Melkein päätä

pyörryttää!" Pääskysparven lailla viserteli poikalauma räystäällä ja
uteliaina, ihaillen korottivat tytöt kaulojansa, silmääräpäyttämättä
seuraten toverien liikkeitä.

"Kiivetkäämme mekin sinne! Yks', kaks', kolme!" huudahti Elli ja

silmänräpäyksessä oli hän jo puolitiessä portailla.

"Ei, ei Elli!" huusivat silloin isä, äiti ja kaikki muut aikaihmiset

verannalta, kauhistunein liikkein vaatien yltiöpäätä heti
laskeutumaan alas. Mutta yritteliä vitkasteli… Siitäkin — puolitiestä
— näki hän jo laajenneen, loistavan maiseman, joka tältä
korkeammalta asteelta katsottuna näytti tuhat kertaa
ihmeellisemmältä, viehättävämmältä, kun esimerkiksi verannan
kaidepuun takaa, taikkapa kellarin katoltakin, — mihinkä joskus
luvallakin oli saanut kiivetä.

"Tule alas! Kuuletko, hetipaikalla alas, sinä pahankurinen lapsi!" Ja

pahankurinen lapsi totteli, tullen alas vaikka verkkaan ja nyrpeän
näköisenä.

"Miks'en minä saa mennä sinne, yhtähyvin kun pojatkin?" nurkui

hän.

"Siksi että se ei sovi tytöille — muista se!" —

Elli painui verannan alimmalle rappuselle istumaan. Äsken niin

iloinen, toiminnanhaluinen lapsensielu oli sumennettu ja
sulkeutuneena mietti se arvoitusta: miksi en minä yhtähyvin kun
pojatkin…

*****

"Se on siis päätetty", sanoi isä tyytyväisesti. "Ja minä toivon

kaikesta sydämestäni, että menestyt lääkäriurallasi Kaarloseni! —
Mutta entäs Esko? On jo aika sinunkin vakiintua siitä, miksi aijot
maailmassa."

"Siitä olen jo kauvan ollut selvillä, isä. Kun poikasena kerran tein
huvihuoneen piirustukset, sanoit sinä että näyttää siltä kun Eskolla
olisi tulevaisuutta tällä alalla ja sitä minulla varmasti onkin! Saat
uskoa, isä, että minä kerran vien arkkitehtuuriamme loistavan
askeleen eteenpäin."

Isä hymyili. "Hyvä, olen siis selvillä ja tyytyväinen lasteni

tulevaisuudesta."

"Mutta minuthan sinä aivan syrjäytät, isä", muistutti Elli "vai eikö
sinua ollenkaan huvita tietää miksi minä aijon?

"Ah sinä! Noo — sinusta kaiketi tulee kunnianarvoisa pikku rouva,

kunhan ennättää — ellet juuri vanhaksi piiaksi aijo", nauroi isä.

Ellin raikkaat kasvot peittyivät synkkiin pilviin ja silmissään loukattu

ihmisarvo salamoi…

"Niin, tuomari Arvolahan on sinuun pahoin pikeytynyt. Ja,

luullakseni, on hänen kainalossaan tulevaisuutesi turvattu", täydensi
Kaarlo.

"Oi, kuinka te olette ilkeitä!" huudahti Elli. "Sekö se siis on tyttöjen

päämäärä ja siihenkö heillä vaan on lupa pyrkiä? 'Tulevaisuus
turvattu'… on se sekin yks' rääsyinen sana! Ikäänkuin meillä ei olisi
oikeutta, niinhyvin kuin velvollisuuttakin, itse, omintakeisesti turvata
tulevaisuuttamme!"

"Sillä tavallahan se asia kuitenkin tavallisesti tässä Jumalan

luomassa maailmassa menee —"
 "Tässä miesten muokkaamassa maailmassa — niin olemme
epäilemättä lähempänä totuutta. Vai luuletteko, uskallatteko luulla
Jumalasta jotain niin alhaista, äärimmäisen ilkeämielistä, että hän
olisi sysännyt naisen siihen alennustilaan, missä tämä vuosituhansia
on saanut värjötellä?"

"Elli, Elli — elä pidä noin suurta suuta. Ehkäpä ne vuosituhannet

juuri kumoavat väitteesi —"

"Mahdollisesti, jos naisasia olisi vieläkin siinä pisteessä, missä se

Aabrahamin aikoina oli — mutta Jumalan kiitos, ne samaiset
vuostuhannet ovat kuitenkin olleet kehityksen, vapautuksen aikoja ja
kieltämättä me olemme matkalla oikeutta, täydellistä tasa-arvoa
kohden, olkoonpa tämä matkamme viimeinen virstapylväs vielä
kuinka kaukana tahansa."

"Sinä olet oikea naisasian agitaattori, Elli!" pisti Kaarlo väliin,

hymyillen ainaista ylimielistä hymyänsä.

"Minulla on kunnia olla! Mutta elä sinä yhtään tuolla tavalla

hymyile… Kuuleppas, se aika on onneksi mennyt, jolloin naisasialle
voitiin vaan hymyillä ja etäällä, etäällä — vaikka tulevassa — on
sekin, jolloin sille enään vaan tarvitaan hymyillä. Nyt on toiminnan,
työn ja taistelun aika!"

"Kiitä Luojaa, lapseni, että elät ajassa, joka sallii sinun nauttia työsi
hedelmiä", lausui äiti. "Minun nuoruudessani saimme tyytyä — ah
emmehän kaikkea uskaltaneet uneksiakaan — mitä te nyt saatte
todellisuudessa omistaa ja nauttia…"

"Ja kuitenkaan, äiti, ei vielä meilläkään ole läheskään kaikkea,

mitä pitäisi olla! — No niin, isä, minä olen päättänyt lukea lääkäriksi
kuten Kaarlokin." —

"Vai päättänyt? Sehän kuuluu erittäin juhlalliselta… Mutta minulta

ei totisesti riitä rahoja siihen, — saan luvan ilmoittaa."

"Vai niin, isä rukka! Olet siis ikuisessa kiitollisuuden velassa

kohtalolle, joka salli kolmannen lapsesi syntyä tytöksi, säästääkseen
kukkaroasi ja estääkseen sen julmuuden tapahtumasta, mikä olisi
ollut välttämätön, jos se kolmaskin olisi ollut poika!"

Isä näytti harmistuneelta, eikä löytänyt pitkään aikaan sanoja

vastineeksi.

"Et sinä toki henno särkeä Ellin tulevaisuutta", sanoi viimein äiti
pyytävän hellästi niinkuin ainakin.

"Te naiset olette niin hiton itsepäisiä toisinaan…"

"Ei isä, kyllä sinulta pitää riittää rahoja Ellillekin, Kaarlon ja minun
on elettävä sitä myöten. Muuten minäkin olen aivan onneton",
lämpeni Esko. "Sehän olisi muuten samaa, kuin jos riistettäisiin Elliltä
vaatteet meille pojille — ja hän työnnettäisiin alastomana pakkaseen!
Se ei saa tapahtua, isä!" —

"Voi tuota Eskoa, sehän on itse olennoitu oikeus ja hyvyys!"

riemuitsi Elli. — "Enkös olekin aina sanonut, että Esko se on, joka
meidän kotimme piirissä edustaa tulevaisuuden herttaista, ylevää,
täydellistynyttä miestä. Tuollaisesta veljestä kannattaa ylpeilläkin!"

Mutta isä vääntelihe nyrpeänä tuolissaan. Hän muistutti suurta

mehiläistä, joka on lentänyt kärpäspaperille ja koettaa turhaan
irroittautua siitä…
 *** END OF THE PROJECT GUTENBERG EBOOK
VASTARANNALLA ***

Updated editions will replace the previous one—the old editions will
be renamed.

Creating the works from print editions not protected by U.S.

copyright law means that no one owns a United States copyright in
these works, so the Foundation (and you!) can copy and distribute it
in the United States without permission and without paying copyright
royalties. Special rules, set forth in the General Terms of Use part of
this license, apply to copying and distributing Project Gutenberg™
electronic works to protect the PROJECT GUTENBERG™ concept
and trademark. Project Gutenberg is a registered trademark, and
may not be used if you charge for an eBook, except by following the
terms of the trademark license, including paying royalties for use of
the Project Gutenberg trademark. If you do not charge anything for
copies of this eBook, complying with the trademark license is very
easy. You may use this eBook for nearly any purpose such as
creation of derivative works, reports, performances and research.
Project Gutenberg eBooks may be modified and printed and given
away—you may do practically ANYTHING in the United States with
eBooks not protected by U.S. copyright law. Redistribution is subject
to the trademark license, especially commercial redistribution.

START: FULL LICENSE

THE FULL PROJECT GUTENBERG LICENSE
 PLEASE READ THIS BEFORE YOU DISTRIBUTE OR USE THIS WORK

To protect the Project Gutenberg™ mission of promoting the free

distribution of electronic works, by using or distributing this work (or
any other work associated in any way with the phrase “Project
Gutenberg”), you agree to comply with all the terms of the Full
Project Gutenberg™ License available with this file or online at
www.gutenberg.org/license.

Section 1. General Terms of Use and

Redistributing Project Gutenberg™
electronic works
1.A. By reading or using any part of this Project Gutenberg™
electronic work, you indicate that you have read, understand, agree
to and accept all the terms of this license and intellectual property
(trademark/copyright) agreement. If you do not agree to abide by all
the terms of this agreement, you must cease using and return or
destroy all copies of Project Gutenberg™ electronic works in your
possession. If you paid a fee for obtaining a copy of or access to a
Project Gutenberg™ electronic work and you do not agree to be
bound by the terms of this agreement, you may obtain a refund from
the person or entity to whom you paid the fee as set forth in
paragraph 1.E.8.

1.B. “Project Gutenberg” is a registered trademark. It may only be

used on or associated in any way with an electronic work by people
who agree to be bound by the terms of this agreement. There are a
few things that you can do with most Project Gutenberg™ electronic
works even without complying with the full terms of this agreement.
See paragraph 1.C below. There are a lot of things you can do with
Project Gutenberg™ electronic works if you follow the terms of this
agreement and help preserve free future access to Project
Gutenberg™ electronic works. See paragraph 1.E below.
1.C. The Project Gutenberg Literary Archive Foundation (“the
Foundation” or PGLAF), owns a compilation copyright in the
collection of Project Gutenberg™ electronic works. Nearly all the
individual works in the collection are in the public domain in the
United States. If an individual work is unprotected by copyright law in
the United States and you are located in the United States, we do
not claim a right to prevent you from copying, distributing,
performing, displaying or creating derivative works based on the
work as long as all references to Project Gutenberg are removed. Of
course, we hope that you will support the Project Gutenberg™
mission of promoting free access to electronic works by freely
sharing Project Gutenberg™ works in compliance with the terms of
this agreement for keeping the Project Gutenberg™ name
associated with the work. You can easily comply with the terms of
this agreement by keeping this work in the same format with its
attached full Project Gutenberg™ License when you share it without
charge with others.

1.D. The copyright laws of the place where you are located also
govern what you can do with this work. Copyright laws in most
countries are in a constant state of change. If you are outside the
United States, check the laws of your country in addition to the terms
of this agreement before downloading, copying, displaying,
performing, distributing or creating derivative works based on this
work or any other Project Gutenberg™ work. The Foundation makes
no representations concerning the copyright status of any work in
any country other than the United States.

1.E. Unless you have removed all references to Project Gutenberg:

1.E.1. The following sentence, with active links to, or other

immediate access to, the full Project Gutenberg™ License must
appear prominently whenever any copy of a Project Gutenberg™
work (any work on which the phrase “Project Gutenberg” appears, or
with which the phrase “Project Gutenberg” is associated) is
accessed, displayed, performed, viewed, copied or distributed:
 This eBook is for the use of anyone anywhere in the United
States and most other parts of the world at no cost and with
almost no restrictions whatsoever. You may copy it, give it away
or re-use it under the terms of the Project Gutenberg License
included with this eBook or online at www.gutenberg.org. If you
are not located in the United States, you will have to check the
laws of the country where you are located before using this
eBook.

1.E.2. If an individual Project Gutenberg™ electronic work is derived

from texts not protected by U.S. copyright law (does not contain a
notice indicating that it is posted with permission of the copyright
holder), the work can be copied and distributed to anyone in the
United States without paying any fees or charges. If you are
redistributing or providing access to a work with the phrase “Project
Gutenberg” associated with or appearing on the work, you must
comply either with the requirements of paragraphs 1.E.1 through
1.E.7 or obtain permission for the use of the work and the Project
Gutenberg™ trademark as set forth in paragraphs 1.E.8 or 1.E.9.

1.E.3. If an individual Project Gutenberg™ electronic work is posted

with the permission of the copyright holder, your use and distribution
must comply with both paragraphs 1.E.1 through 1.E.7 and any
additional terms imposed by the copyright holder. Additional terms
will be linked to the Project Gutenberg™ License for all works posted
with the permission of the copyright holder found at the beginning of
this work.

1.E.4. Do not unlink or detach or remove the full Project

Gutenberg™ License terms from this work, or any files containing a
part of this work or any other work associated with Project
Gutenberg™.

1.E.5. Do not copy, display, perform, distribute or redistribute this

electronic work, or any part of this electronic work, without
prominently displaying the sentence set forth in paragraph 1.E.1 with
active links or immediate access to the full terms of the Project
Gutenberg™ License.
1.E.6. You may convert to and distribute this work in any binary,
compressed, marked up, nonproprietary or proprietary form,
including any word processing or hypertext form. However, if you
provide access to or distribute copies of a Project Gutenberg™ work
in a format other than “Plain Vanilla ASCII” or other format used in
the official version posted on the official Project Gutenberg™ website
(www.gutenberg.org), you must, at no additional cost, fee or expense
to the user, provide a copy, a means of exporting a copy, or a means
of obtaining a copy upon request, of the work in its original “Plain
Vanilla ASCII” or other form. Any alternate format must include the
full Project Gutenberg™ License as specified in paragraph 1.E.1.

1.E.7. Do not charge a fee for access to, viewing, displaying,

performing, copying or distributing any Project Gutenberg™ works
unless you comply with paragraph 1.E.8 or 1.E.9.

1.E.8. You may charge a reasonable fee for copies of or providing

access to or distributing Project Gutenberg™ electronic works
provided that:

• You pay a royalty fee of 20% of the gross profits you derive from
the use of Project Gutenberg™ works calculated using the
method you already use to calculate your applicable taxes. The
fee is owed to the owner of the Project Gutenberg™ trademark,
but he has agreed to donate royalties under this paragraph to
the Project Gutenberg Literary Archive Foundation. Royalty
payments must be paid within 60 days following each date on
which you prepare (or are legally required to prepare) your
periodic tax returns. Royalty payments should be clearly marked
as such and sent to the Project Gutenberg Literary Archive
Foundation at the address specified in Section 4, “Information
about donations to the Project Gutenberg Literary Archive
Foundation.”

• You provide a full refund of any money paid by a user who

notifies you in writing (or by e-mail) within 30 days of receipt that
s/he does not agree to the terms of the full Project Gutenberg™
 License. You must require such a user to return or destroy all
copies of the works possessed in a physical medium and
discontinue all use of and all access to other copies of Project
Gutenberg™ works.

• You provide, in accordance with paragraph 1.F.3, a full refund of

any money paid for a work or a replacement copy, if a defect in
the electronic work is discovered and reported to you within 90
days of receipt of the work.

• You comply with all other terms of this agreement for free
distribution of Project Gutenberg™ works.

1.E.9. If you wish to charge a fee or distribute a Project Gutenberg™

electronic work or group of works on different terms than are set
forth in this agreement, you must obtain permission in writing from
the Project Gutenberg Literary Archive Foundation, the manager of
the Project Gutenberg™ trademark. Contact the Foundation as set
forth in Section 3 below.

1.F.

1.F.1. Project Gutenberg volunteers and employees expend

considerable effort to identify, do copyright research on, transcribe
and proofread works not protected by U.S. copyright law in creating
the Project Gutenberg™ collection. Despite these efforts, Project
Gutenberg™ electronic works, and the medium on which they may
be stored, may contain “Defects,” such as, but not limited to,
incomplete, inaccurate or corrupt data, transcription errors, a
copyright or other intellectual property infringement, a defective or
damaged disk or other medium, a computer virus, or computer
codes that damage or cannot be read by your equipment.

1.F.2. LIMITED WARRANTY, DISCLAIMER OF DAMAGES - Except

for the “Right of Replacement or Refund” described in paragraph
1.F.3, the Project Gutenberg Literary Archive Foundation, the owner
of the Project Gutenberg™ trademark, and any other party
distributing a Project Gutenberg™ electronic work under this
agreement, disclaim all liability to you for damages, costs and
expenses, including legal fees. YOU AGREE THAT YOU HAVE NO
REMEDIES FOR NEGLIGENCE, STRICT LIABILITY, BREACH OF
WARRANTY OR BREACH OF CONTRACT EXCEPT THOSE
PROVIDED IN PARAGRAPH 1.F.3. YOU AGREE THAT THE
FOUNDATION, THE TRADEMARK OWNER, AND ANY
DISTRIBUTOR UNDER THIS AGREEMENT WILL NOT BE LIABLE
TO YOU FOR ACTUAL, DIRECT, INDIRECT, CONSEQUENTIAL,
PUNITIVE OR INCIDENTAL DAMAGES EVEN IF YOU GIVE
NOTICE OF THE POSSIBILITY OF SUCH DAMAGE.

1.F.3. LIMITED RIGHT OF REPLACEMENT OR REFUND - If you

discover a defect in this electronic work within 90 days of receiving it,
you can receive a refund of the money (if any) you paid for it by
sending a written explanation to the person you received the work
from. If you received the work on a physical medium, you must
return the medium with your written explanation. The person or entity
that provided you with the defective work may elect to provide a
replacement copy in lieu of a refund. If you received the work
electronically, the person or entity providing it to you may choose to
give you a second opportunity to receive the work electronically in
lieu of a refund. If the second copy is also defective, you may
demand a refund in writing without further opportunities to fix the
problem.

1.F.4. Except for the limited right of replacement or refund set forth in
paragraph 1.F.3, this work is provided to you ‘AS-IS’, WITH NO
OTHER WARRANTIES OF ANY KIND, EXPRESS OR IMPLIED,
INCLUDING BUT NOT LIMITED TO WARRANTIES OF
MERCHANTABILITY OR FITNESS FOR ANY PURPOSE.

1.F.5. Some states do not allow disclaimers of certain implied

warranties or the exclusion or limitation of certain types of damages.
If any disclaimer or limitation set forth in this agreement violates the
law of the state applicable to this agreement, the agreement shall be
interpreted to make the maximum disclaimer or limitation permitted
by the applicable state law. The invalidity or unenforceability of any
provision of this agreement shall not void the remaining provisions.

1.F.6. INDEMNITY - You agree to indemnify and hold the

Foundation, the trademark owner, any agent or employee of the
Foundation, anyone providing copies of Project Gutenberg™
electronic works in accordance with this agreement, and any
volunteers associated with the production, promotion and distribution
of Project Gutenberg™ electronic works, harmless from all liability,
costs and expenses, including legal fees, that arise directly or
indirectly from any of the following which you do or cause to occur:
(a) distribution of this or any Project Gutenberg™ work, (b)
alteration, modification, or additions or deletions to any Project
Gutenberg™ work, and (c) any Defect you cause.

Section 2. Information about the Mission of

Project Gutenberg™
Project Gutenberg™ is synonymous with the free distribution of
electronic works in formats readable by the widest variety of
computers including obsolete, old, middle-aged and new computers.
It exists because of the efforts of hundreds of volunteers and
donations from people in all walks of life.

Volunteers and financial support to provide volunteers with the

assistance they need are critical to reaching Project Gutenberg™’s
goals and ensuring that the Project Gutenberg™ collection will
remain freely available for generations to come. In 2001, the Project
Gutenberg Literary Archive Foundation was created to provide a
secure and permanent future for Project Gutenberg™ and future
generations. To learn more about the Project Gutenberg Literary
Archive Foundation and how your efforts and donations can help,
see Sections 3 and 4 and the Foundation information page at
www.gutenberg.org.
 Section 3. Information about the Project
Gutenberg Literary Archive Foundation
The Project Gutenberg Literary Archive Foundation is a non-profit
501(c)(3) educational corporation organized under the laws of the
state of Mississippi and granted tax exempt status by the Internal
Revenue Service. The Foundation’s EIN or federal tax identification
number is 64-6221541. Contributions to the Project Gutenberg
Literary Archive Foundation are tax deductible to the full extent
permitted by U.S. federal laws and your state’s laws.

The Foundation’s business office is located at 809 North 1500 West,

Salt Lake City, UT 84116, (801) 596-1887. Email contact links and up
to date contact information can be found at the Foundation’s website
and official page at www.gutenberg.org/contact

Section 4. Information about Donations to

the Project Gutenberg Literary Archive
Foundation
Project Gutenberg™ depends upon and cannot survive without
widespread public support and donations to carry out its mission of
increasing the number of public domain and licensed works that can
be freely distributed in machine-readable form accessible by the
widest array of equipment including outdated equipment. Many small
donations ($1 to $5,000) are particularly important to maintaining tax
exempt status with the IRS.

The Foundation is committed to complying with the laws regulating

charities and charitable donations in all 50 states of the United
States. Compliance requirements are not uniform and it takes a
considerable effort, much paperwork and many fees to meet and
keep up with these requirements. We do not solicit donations in
locations where we have not received written confirmation of
compliance. To SEND DONATIONS or determine the status of
compliance for any particular state visit www.gutenberg.org/donate.

While we cannot and do not solicit contributions from states where

we have not met the solicitation requirements, we know of no
prohibition against accepting unsolicited donations from donors in
such states who approach us with offers to donate.

International donations are gratefully accepted, but we cannot make

any statements concerning tax treatment of donations received from
outside the United States. U.S. laws alone swamp our small staff.

Please check the Project Gutenberg web pages for current donation
methods and addresses. Donations are accepted in a number of
other ways including checks, online payments and credit card
donations. To donate, please visit: www.gutenberg.org/donate.

Section 5. General Information About Project

Gutenberg™ electronic works
Professor Michael S. Hart was the originator of the Project
Gutenberg™ concept of a library of electronic works that could be
freely shared with anyone. For forty years, he produced and
distributed Project Gutenberg™ eBooks with only a loose network of
volunteer support.

Project Gutenberg™ eBooks are often created from several printed

editions, all of which are confirmed as not protected by copyright in
the U.S. unless a copyright notice is included. Thus, we do not
necessarily keep eBooks in compliance with any particular paper
edition.

Most people start at our website which has the main PG search
facility: www.gutenberg.org.

This website includes information about Project Gutenberg™,

including how to make donations to the Project Gutenberg Literary
Archive Foundation, how to help produce our new eBooks, and how
to subscribe to our email newsletter to hear about new eBooks.