Clathrate Hydrates: Molecular Science

and Characterization, 2 Volumes John

A. Ripmeester
Visit to download the full and correct content document:
https://ebookmass.com/product/clathrate-hydrates-molecular-science-and-characteriz
ation-2-volumes-john-a-ripmeester/
Clathrate Hydrates
Clathrate Hydrates

Molecular Science and Characterization

Volume 1

Edited by

John A. Ripmeester
Saman Alavi
Clathrate Hydrates

Molecular Science and Characterization

Volume 2

Edited by

John A. Ripmeester
Saman Alavi
Editors
Dr. John A. Ripmeester
National Research Council of Canada
100 Sussex Dr.
K1A 0R6 NK
Canada
Dr. Saman Alavi
University of Ottawa
Department of Chemistry and
Biomolecular Sciences
STEM Complex, 150 Louis-Pasteur Pvt.
Ottawa, ON, K1N 6N5
Canada
Cover Images: © Structure illustration
provided by Dr. Satoshi Takeya; inset
image © metamorworks/Shutterstock
All books published by WILEY-VCH are carefully
produced. Nevertheless, authors, editors, and
publisher do not warrant the information
contained in these books, including this book,
to be free of errors. Readers are advised to keep
in mind that statements, data, illustrations,
procedural details or other items may
inadvertently be inaccurate.
Library of Congress Card No.: applied for
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available
from the British Library.
Bibliographic information published by
the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists
this publication in the Deutsche
Nationalbibliografie; detailed bibliographic
data are available on the Internet at
<http://dnb.d-nb.de>.
© 2022 WILEY-VCH GmbH, Boschstr. 12,
69469 Weinheim, Germany
All rights reserved (including those of
translation into other languages). No part of
this book may be reproduced in any form – by
photoprinting, microfilm, or any other
means – nor transmitted or translated into a
machine language without written permission
from the publishers. Registered names,
trademarks, etc. used in this book, even when
not specifically marked as such, are not to be
considered unprotected by law.
Print ISBN: 978-3-527-33984-6
ePDF ISBN: 978-3-527-69508-9
ePub ISBN: 978-3-527-69506-5
oBook ISBN: 978-3-527-69505-8
Typesetting Straive, Chennai, India
Printing and Binding
Printed on acid-free paper
10 9 8 7 6 5 4 3 2 1
To my wife Beth and daughters Heather and Wendy who put up with my
science-oriented adventures that sometimes got in the way of family time, to the
memory of my parents, John and Thea, who, while raising their recently emigrated
family, encouraged me to pursue higher education.

To my wife Dorothy for her support and patience during my never-ending scientific
activities, to my mother Zari for her encouragement on our path to higher education,
and to the memory of my father Mohammad who motivated me to become a chemist.
 vii

Contents

Volume 1

Preface xiii

1 An Introduction to Clathrate Hydrate Science 1

John A. Ripmeester, Saman Alavi, and Christopher I. Ratcliffe
1.1 Introduction 1
1.2 Selected Highlights of Clathrate Hydrate Science Research Up to the
Present 4
1.3 Clathrate Hydrate Research at the NRC Canada 10
1.4 Contributors to NRC Clathrate Hydrate Research 21
1.5 Review Articles and Books on Clathrate Hydrates 23
1.6 Conference Proceedings 25
1.6.1 Canadian Permafrost Conference 25
1.6.2 Physics and Chemistry of Ice 25
1.6.3 International Conference on Gas Hydrates (IGCH) Proceedings 26

2 An Introduction to Clathrate Hydrates 27

John A. Ripmeester and Saman Alavi
2.1 Introduction 27
2.2 The First Gas Hydrates 28
2.3 The Phase Rule 34
2.4 de Forcrand and Villard – Career Gas Hydrate Researchers 38
2.5 Nikitin and von Stackelberg 48
2.6 Solving the Gas Hydrate Puzzle 50
2.7 Clathrate Hydrate Science – A New Era 54
2.8 Clathrate Hydrates in Engineering 54
2.9 Clathrate Hydrates in Nature 55
2.10 Summary and Observations 56
References 57
viii Contents

3 Classification of Clathrate Hydrates 65

John A. Ripmeester, Satoshi Takeya, and Saman Alavi
3.1 Introduction 65
3.2 Hydrates as Clathrates 65
3.3 Clathrate and Related Hydrates – Guest Chemistry 66
3.4 The Canonical Clathrate Hydrates 72
3.4.1 Polyhedra and Filling Three-Dimensional Space 73
3.4.2 Filling the Polyhedra 75
3.5 Phase Equilibria 85
3.5.1 Simple Hydrates 85
3.5.2 Double and Mixed Hydrates, Natural Gas Hydrates 90
3.6 Tabulation of Hydrate Properties 97
3.6.1 Simple Clathrate Hydrates 97
3.6.2 CS-II (sII) Double Hydrates (Guests that Require a Help Gas for
Stability) 98
3.6.3 HS-III (sH) Hydrate Guests 98
3.7 Summary 98
References 98

4 Synthesis of Clathrate Hydrates 123

John A. Ripmeester and Saman Alavi
4.1 Introduction 123
4.2 General Considerations in the Synthesis of Clathrate Hydrates 123
4.2.1 A Complex Process 123
4.2.2 Air Entrainment 124
4.3 Synthesis of Hydrates with Water-Soluble Guests Near Ambient
Conditions 125
4.3.1 Hydrates with Congruent Melting Points 125
4.3.2 Hydrates with Incongruent Melting Points 125
4.4 Synthesis of Hydrates of Guests with Low Solubility in Water 126
4.4.1 Low-Pressure Methods: Water–Liquid Guest and Water–Gaseous Guest
Reactions 126
4.4.2 Powdered Ice Reactions with Liquid or Gaseous Guests 127
4.5 Synthesis of Clathrate Hydrates of Strongly Hydrated or Reactive
Guests 128
4.6 Pure Hydrates – Kinetic and Thermodynamic Control 128
4.7 High-Pressure Reactors 131
4.7.1 Stirred Reactors 131
4.7.2 Stationary (Non-stirred) Reactors 131
4.7.3 Other Setups for Hydrate Synthesis – Bubble Columns, Spray
Reactors 131
4.8 Synthesis of Single Crystals 134
4.9 Summary 137
References 138
 Contents ix

5 Structures of Canonical Clathrate Hydrates 141

John A. Ripmeester, Satoshi Takeya, and Saman Alavi
5.1 Introduction 141
5.2 The Canonical Clathrate Hydrates 141
5.2.1 General Structural Properties 141
5.2.2 Geometry of Unit Cells and Cages: CS-I, CS-II, and HS-III 147
5.2.2.1 Structural Features CS-I, CS-II, and HS-III Clathrate Hydrates 147
5.2.2.2 Correlation of Guest Size with Unit Cell Dimensions 151
5.2.2.3 Flexible Guest Molecules Showing Conformational Isomerism 152
5.2.2.4 Location of Guest Molecules in the Cages 153
5.2.2.5 Effects of Hydrogen Bonding on Cage Structure and Guest–Water
Interactions 158
5.2.2.6 Halogen–Water Interactions in Clathrate Hydrates (Chlorine) 160
5.2.2.7 Polymorphism 161
5.2.3 Geometry of Unit Cell and Cages: Tetragonal Bromine Hydrate
(TS-I) 164
5.2.4 Geometry of Unit Cell and Cages: Dimethyl Ether Hydrate (TrS-I) 165
5.2.5 Geometry of Unit Cell and Cages: Xe Hydrate (HS-I) 166
5.3 Some General Structural Considerations 168
5.3.1 Tiling in Three-Dimensional Space – Frank–Kasper and Weaire–Phelan
Polyhedra 168
5.3.2 Schlegel Diagrams 177
5.3.3 Polytypism 178
5.3.3.1 Hydrate Structures as Layered Polytypes 178
5.3.4 Materials with Structural Features in Common with Clathrate
Hydrates 181
References 182

6 Structures of Noncanonical Clathrates and Related

Hydrates 189
John A. Ripmeester, Satoshi Takeya, and Saman Alavi
6.1 Introduction 189
6.2 Amine Hydrates 189
6.3 Ionic Clathrate Hydrates 194
6.3.1 Salt Hydrates 194
6.3.1.1 Salt Hydrates – Cations as Large Cage Guests 194
6.3.1.2 Salt Hydrates – Cations as Large Cage Guests, Neutral Small Cage
Guests 199
6.3.1.3 Salt Hydrates – Cations as Small-Cage Guests 201
6.3.2 Hydrates of Strong Acids 202
6.3.3 Hydrates of Strong Bases 204
6.3.4 Ionic Clathrate Hydrates with Heterogeneous Frameworks 209
6.3.5 Clathrates with H2 O–NH4 F Solid Solution Frameworks 209
References 211
x Contents

7 Thermodynamics and Statistical Mechanics of Clathrate

Hydrates 219
John A. Ripmeester and Saman Alavi
7.1 Introduction 219
7.2 Clathrate Hydration Numbers and Cage Occupancies 219
7.2.1 Direct Measurement of Hydration Numbers 220
7.2.2 Thermodynamic Methods to Determine Guest Occupancy 228
7.2.2.1 The Clapeyron and Clausius–Clapeyron Equations and the Use of Phase
Equilibria 228
7.2.2.2 The Miller–Strong Method and Effects of Solutes on Phase
Equilibria 230
7.2.2.3 Calorimetry and Other Instrumental Methods in Conjunction with
Thermodynamic Methods 230
7.3 Enthalpy of Dissociation of Hydrate Phases 231
7.4 Statistical Mechanics of Clathrate Hydrates: The van der
Waals–Platteeuw Solid Solution Model for Clathrate Hydrate
Formation 232
7.5 Application of the van der Waals–Platteeuw Theory to Determining
Hydrate Equilibrium Composition 237
7.5.1 Using van der Waals–Platteeuw Theory to Determine Cage
Occupancies 237
7.5.2 Instrumental Methods in Conjunction with the van der Waals–Platteeuw
Theory to Determine Occupation Fractions 239
7.5.2.1 Solid-State NMR 240
7.5.2.2 Raman Spectroscopy 243
7.5.2.3 Diffraction Methods 243
7.5.3 Some General Conclusions and Nonstoichiometry of Clathrate
Hydrates 246
7.6 Computational Predictions of Hydrate Dissociation Pressures Using the
van der Waals–Platteeuw Theory 247
7.7 Extensions of the van der Waals–Platteeuw Theory 254
7.7.1 Multiple Cage Occupancies and Guest Mixtures 254
7.7.2 Relaxing Some Position Restraints on Cage Water Molecules 255
7.7.3 Relaxing the Constraint of Constant Volume on the Hydrate Phase 255
7.7.4 Validity of the Basic van der Waals–Platteeuw Theory 258
7.8 Other Thermodynamic Topics 260
7.8.1 Encagement Enthalpy 260
7.8.2 Thermodynamic Inhibitors to Hydrate Formation 263
7.8.3 Compositional Tuning in Clathrate Hydrates 265
7.8.4 Transitions Between Binary CS-II and HS-III Binary Hydrates to Pure
CS-I Hydrates for Small Guest Molecules 266
7.8.5 A Lower Critical Decomposition Temperature 270
7.9 Conclusions 271
References 272
 Contents xi

Volume 2

Preface xv

8 Molecular Simulations of Clathrate Hydrates 283

Saman Alavi and John A. Ripmeester

9 X-ray and Neutron Diffraction and Scattering of Clathrate

Hydrates 369
John S. Tse, Dennis D. Klug, and Satoshi Takeya

10 Characterization of Clathrate Hydrates Using Nuclear

Magnetic Resonance Spectroscopy 417
Christopher I. Ratcliffe, Igor L. Moudrakovski, and John A. Ripmeester

11 Specialized Methods of Nuclear Magnetic Resonance

Spectroscopy and Magnetic Resonance Imaging Applied to
Characterization of Clathrate Hydrates 467
Igor L. Moudrakovski, Christopher I. Ratcliffe, and John A. Ripmeester

12 Reorientation and Diffusion in Clathrate Hydrates 513

John A. Ripmeester, Christopher I. Ratcliffe, Igor L. Moudrakovski, and
Saman Alavi

13 IR and Raman Spectroscopy of Clathrate Hydrates 569

Tsutomu Uchida and Amadeu K. Sum

14 Kinetics of Clathrate Hydrate Processes 631

Peter Englezos, Saman Alavi, and John A. Ripmeester

15 Mechanical and Thermal Transport Properties of Clathrate

Hydrates 717
John S. Tse and Dennis D. Klug

16 Applications of Clathrate (Gas) Hydrates 749

Peter Englezos

Index 783
 vii

Contents

Volume 1

Preface xiii

1 An Introduction to Clathrate Hydrate Science 1

John A. Ripmeester, Saman Alavi, and Christopher I. Ratcliffe

2 An Introduction to Clathrate Hydrates 27

John A. Ripmeester and Saman Alavi

3 Classification of Clathrate Hydrates 65

John A. Ripmeester, Satoshi Takeya, and Saman Alavi

4 Synthesis of Clathrate Hydrates 123

John A. Ripmeester and Saman Alavi

5 Structures of Canonical Clathrate Hydrates 141

John A. Ripmeester, Satoshi Takeya, and Saman Alavi

6 Structures of Noncanonical Clathrates and Related

Hydrates 189
John A. Ripmeester, Satoshi Takeya, and Saman Alavi

7 Thermodynamics and Statistical Mechanics of Clathrate

Hydrates 219
John A. Ripmeester and Saman Alavi
viii Contents

Volume 2

Preface xv

8 Molecular Simulations of Clathrate Hydrates 283

Saman Alavi and John A. Ripmeester
8.1 Introduction 283
8.2 Molecular Simulations 284
8.2.1 Classical Molecular Dynamics Simulations 284
8.2.2 Monte Carlo Simulations of Clathrate Hydrates 287
8.2.3 Ab Initio Molecular Dynamics Simulations 288
8.2.4 Classical Interaction Potentials for Simulating Clathrate Hydrates 289
8.2.5 Proton Arrangements in the Clathrate Hydrate Simulations 293
8.3 Structural Characterization of Clathrate Hydrates with Simulations 295
8.3.1 Radial Distribution Functions 296
8.3.2 Lattice Constants and Three-Phase Equilibrium Lines 298
8.3.3 Guest Distribution and Structure in Cages 299
8.3.4 Order Parameters and Characterization of Clathrate Hydrate, Ice, and
Water Phases 302
8.3.5 Guest–Host Hydrogen Bonding in Clathrate Hydrate Cages 307
8.4 Dynamic Characterizations of Guest Motion in Cages 308
8.4.1 Velocity and Orientation Autocorrelation Functions 309
8.5 Simulations of Clathrate Hydrates 311
8.5.1 Mechanisms of Hydrate Decomposition, Nucleation, and Growth 312
8.5.2 Enthalpy of Formation, Decomposition, and Encagement from
Molecular Simulations 331
8.6 Ab Initio Quantum Mechanical Calculations of Clathrate Hydrates 334
8.6.1 Stationary Quantum States of Small Guests in Cages 335
8.6.2 Ab Initio Molecular Dynamics 340
8.7 Conclusions and Outlook 341
References 342

9 X-ray and Neutron Diffraction and Scattering of Clathrate

Hydrates 369
John S. Tse, Dennis D. Klug, and Satoshi Takeya
9.1 Introduction 369
9.2 Crystallography and X-ray Diffraction 370
9.2.1 Comments on Diffraction as Applied to Hydrate Structure
Determination 373
9.2.1.1 Single-Crystal Diffraction 373
9.2.1.2 Powder Diffraction 374
9.3 Instrumentation 375
9.4 Structural Characterization with Diffraction Methods 379
9.4.1 Diffraction and Structure–Guest Size Relationship 380
 Contents ix

9.4.2 Unconventional Applications of Diffraction 384

9.5 Neutron Diffraction or Elastic Neutron Scattering 390
9.6 Inelastic Neutron Scattering 396
9.7 Inelastic X-ray Scattering 400
9.8 Summary 407
References 407

10 Characterization of Clathrate Hydrates Using Nuclear

Magnetic Resonance Spectroscopy 417
Christopher I. Ratcliffe, Igor L. Moudrakovski, and John A. Ripmeester
10.1 Introduction 417
10.2 NMR Interactions 418
10.2.1 The Zeeman Interaction 418
10.2.2 Other Interactions 420
10.2.2.1 The Shielding Interaction (σ) and Chemical Shift (δ) 420
10.2.2.2 The Nuclear Dipole–Dipole Interaction 423
10.2.2.3 The Spin–Spin J-Coupling Interaction 424
10.2.2.4 The Quadrupolar Coupling Interaction 424
10.2.2.5 The Spin–Rotation Coupling Interaction 427
10.2.2.6 Interactions with Unpaired Electrons 427
10.2.3 Units 427
10.3 Experimental Aspects of NMR Spectroscopy 427
10.3.1 The Basic NMR Experiment 427
10.3.2 Techniques for Enhancing Sensitivity and Resolution 428
10.3.2.1 Dipolar Decoupling 428
10.3.2.2 Magic Angle Spinning, MAS 429
10.3.2.3 Cross-Polarization (CP) 430
10.3.2.4 Hyperpolarization of 129 Xe (HP Xe) 430
10.4 The Development of NMR Techniques Over Time 430
10.5 NMR Powder Line Shapes in Clathrate Hydrates 432
10.5.1 Dipolar Line Shapes 432
10.5.1.1 Magnetic Dilution 432
10.5.1.2 Two-Spin Systems 432
10.5.1.3 Three-Spin Systems 433
10.5.1.4 Four-Spin Systems 434
10.5.1.5 Six-Spin Systems 434
10.5.1.6 Multi-Spin Systems 436
10.5.1.7 Effects of Paramagnetic Oxygen on 1 H Line Shapes 436
10.5.2 Chemical Shift Line Shapes 437
10.5.2.1 129 Xe NMR 437

10.5.2.2 Chemical Shift Line Shapes of Other Nuclei: 77 Se, 31 P, 19 F, 13 C 444

10.5.3 Quadrupolar Line Shapes 446
10.5.3.1 Spin 1: Deuterium 2 H 446
10.5.3.2 Half-Integer Quadrupolar Nuclei (131 Xe, 83 Kr, 33 S, 17 O) 450
References 458
x Contents

11 Specialized Methods of Nuclear Magnetic Resonance

Spectroscopy and Magnetic Resonance Imaging Applied to
Characterization of Clathrate Hydrates 467
Igor L. Moudrakovski, Christopher I. Ratcliffe, and John A. Ripmeester
11.1 Introduction 467
13 C MAS NMR in Compositional and Structural Analysis of Gas
11.2
Hydrates 468
11.2.1 Experimental Considerations 468
11.2.2 Overview of 13 C MAS NMR in Clathrate Hydrates 470
11.2.3 Concluding Remarks and Outlook 482
11.3 129 Xe NMR Applications: Other Topics 482

11.3.1 Transient/Metastable Phases 482

11.3.2 Rapid Scanning of the Formation of CS-I Xe Hydrate from Ice with
Hyperpolarized Xe 483
11.3.3 Annealing of Co-deposits of Xe and H2 O 485
11.3.4 H2 O-NH4 F Solid Solution Frameworks 485
11.4 Ionic Hydrates 486
11.4.1 Hydrates of Alkylammonium Salts 486
11.4.2 Hydrates of Strong Acids 487
11.4.3 Hydrates of Strong Bases 487
11.5 Clathrate Hydrates and Magnetic Resonance Imaging 489
11.5.1 Information About Gas Hydrates Accessible by Magnetic Resonance
Imaging 490
11.5.2 Experimental Conditions and Equipment for MRI in Gas
Hydrates 493
11.5.3 Overview of Current MRI Applications in Gas Hydrate
Research 495
11.5.4 Concluding Remarks and Outlook 502
References 503

12 Reorientation and Diffusion in Clathrate Hydrates 513

John A. Ripmeester, Christopher I. Ratcliffe, Igor L. Moudrakovski, and
Saman Alavi
12.1 Introduction 513
12.2 Early Work on Clathrates/Inclusion Compounds 514
12.3 Dynamics 515
12.3.1 Dynamics and Timescales 515
12.3.2 Dielectric Relaxation 516
12.3.3 NMR Spectroscopy 519
12.3.3.1 Nuclear Dipolar Coupling 519
12.3.3.2 Nuclear Quadrupolar Interactions 522
12.3.3.3 Chemical Shift Line shapes 524
12.4 Water Dynamics in Ice and Clathrate Hydrates 525
12.4.1 Water Dynamics in Ice Ih 525
12.4.2 Water Dynamics in Clathrate Hydrates 528
 Contents xi

12.5 Guest Motions 534

12.5.1 Guest Reorientation: General Considerations 534
12.5.1.1 Reorientation of Spherical Top Guest Molecules 536
12.5.1.2 Reorientation of Symmetric Top Guest Molecules 539
12.5.1.3 Reorientation of Asymmetric Top Guest Molecules 544
12.5.2 Diffusion 550
12.5.3 Nonclassical Dynamics 554
12.5.3.1 Methyl Groups 554
12.5.3.2 Dynamics of Light Tetrahedral Molecules 556
12.6 Summary 557
References 559

13 IR and Raman Spectroscopy of Clathrate Hydrates 569

Tsutomu Uchida and Amadeu K. Sum
13.1 Fundamentals and Quantification 570
13.2 IR Spectroscopy of Clathrate Hydrates 577
13.2.1 Far IR Transmission – FT-IR on Vapor-Deposited Thin Films 577
13.2.2 Recent Studies of Clathrate Hydrates Using IR Spectroscopy 578
13.3 Raman Spectroscopy of Clathrate Hydrates 581
13.3.1 Guest Molecule Information 582
13.3.1.1 Detection of Encapsulation 582
13.3.1.2 Quantification of Raman Peak Positions 585
13.3.1.3 Quantification of Cage Occupancy 588
13.3.1.4 Application of Raman Spectroscopy to Kinetic Processes 591
13.3.1.5 Analysis of Natural Hydrate Samples 593
13.3.2 Noncontact, Non-destructive Measurements of Gas Hydrates Via Visible
Light 596
13.3.2.1 Application of Raman Spectroscopy to Clathrate Hydrate Kinetic
Studies 596
13.3.2.2 Gas Hydrate Phases Obtained under High-Pressure Conditions 600
13.3.2.3 In Situ Analysis of Natural Hydrate Sample Under Deep Sea
Condition 605
13.4 Conclusions 605
References 614

14 Kinetics of Clathrate Hydrate Processes 631

Peter Englezos, Saman Alavi, and John A. Ripmeester
14.1 Introduction 631
14.2 Experimental Measurement of Hydrate Process Rates 631
14.2.1 Kinetics – Gas Uptake Measurements 631
14.2.2 Kinetics of CS-1 and CS-II hydrates 633
14.2.3 Kinetics of HS-III Hydrates 636
14.2.4 Kinetics Measurements – Other Methods 637
14.2.5 Average and Spatially Localized Kinetics 641
14.3 Modeling the Kinetics of Hydrate Nucleation 645
xii Contents

14.3.1 Hydrate Formation 645

14.3.2 Homogeneous Nucleation 647
14.3.3 Heterogeneous Nucleation 652
14.3.4 Validity and Relevance of Classical Nucleation Theory 655
14.4 Hydrate Phase Transformations 660
14.4.1 Hydrate Growth from Water 660
14.4.2 Hydrate Growth from Ice 664
14.4.2.1 The Shrinking Core Model 665
14.4.2.2 The Avrami Equation 667
14.4.3 Hydrate Crystal Morphology 673
14.4.4 Hydrate Decomposition 676
14.5 Metastability 678
14.6 Kinetic Modifiers 680
14.6.1 Surfactants 680
14.6.2 Defect Generation in the Hydrogen-Bonded Ice and Hydrate
Lattices 682
14.6.3 Kinetic Hydrate Inhibitors 683
14.6.3.1 Macroscopic Descriptions of Hydrate Inhibition 683
14.6.3.2 Mechanism of Kinetic Inhibition 684
14.6.3.3 Complexities of the Hydrate Inhibition Process 688
14.7 Molecular Simulations of Clathrate Hydrate Nucleation and
Growth 690
14.7.1 Simulations of Heterogeneous Nucleation 691
14.7.2 Molecular Simulations of Homogeneous Nucleation 692
14.7.3 Simulations of Hydrate Growth 695
14.7.4 Simulations of Hydrate Growth and Decomposition in the Presence of
Inhibitors 696
14.8 Concluding Remarks 697
References 698

15 Mechanical and Thermal Transport Properties of Clathrate

Hydrates 717
John S. Tse and Dennis D. Klug
15.1 Introduction 717
15.2 Theoretical Background 718
15.2.1 Elastic Moduli 718
15.2.2 Thermal Conductivity 720
15.3 Mechanical Properties: Acoustic Velocity and Elastic Constants 721
15.4 Thermal Expansion 730
15.5 Transport Properties: Thermal Conductivity 734
15.6 Molecular Dynamics Simulations of Thermal Properties of Clathrate
Hydrates 739
15.7 Summary 742
References 743
 Contents xiii

16 Applications of Clathrate (Gas) Hydrates 749

Peter Englezos
16.1 Introduction 749
16.2 Flow Assurance in Oil and Gas Pipelines 750
16.2.1 Large-Scale Flow Loops 753
16.2.2 Catastrophic Hydrate Formation and Pipeline Plug Potential 754
16.2.3 Oil and Gas Pipelines with Hydrophobic Surfaces 754
16.3 Natural Gas Energy Recovery from the Earth’s Hydrates 755
16.3.1 Extraction of Natural Gas by Injection of CO2 or CO2 /N2 Flue Gas 757
16.4 Desalination 758
16.5 Concentration of Wastewater and Aqueous Organic Solutions 759
16.6 Storage and Transportation of Natural Gas, Hydrogen, and Other
Materials 760
16.6.1 Natural Gas Storage 760
16.6.2 Hydrogen Storage 762
16.7 Gas Separations 765
16.7.1 Metrics 766
16.7.2 Separation of CO2 from Flue Gas Mixtures (Post-Combustion
Capture) 767
16.7.2.1 Impact of SO2 768
16.7.3 Separation of CO2 from Fuel Gas Mixtures (Pre-Combustion
Capture) 768
16.7.4 Other Gas Separations 771
16.8 Conclusions 772
References 772

Index 783
 xiii

Preface

Scope
Why write this book? A number of reasons come to mind. Today, a vast number of
publications on clathrate hydrates continue to appear in journals dealing with the
many different, often non-overlapping areas of hydrate research. Increasingly, these
studies focus especially on engineering and geological aspects, as well as potential
applications. Molecular science has provided the fundamental underpinnings for
much of this work; however, the earlier work has become more difficult to find, and
there have not been major comprehensive monographs or books focused on scien-
tific aspects of these substances for some 40 years. It is to fill this gap that preparation
of this book was undertaken. We also feel there are a number of misconceptions or
questionable approaches that have propagated over the years, and this book provides
an opportunity to revisit some of these points.
The 150 years that it took for the first observed phenomenon of gas hydrates to
be properly explained make for a fascinating story of the intertwining of the then
current hydrate science, advances in technology, and the evolution of chemical
concepts. After an Introduction and summary of the “classical period,” the book
presents 16 chapters outlining hydrate science in different areas of specialization
(see below). Each chapter provides a short summary of the respective methodology
and is written with an emphasis on the experience of the authors with significant
feedback from the editors and the other chapter authors. The book also provides
comprehensive tabulated information on the structural, compositional, spectro-
scopic, thermodynamic properties, and molecular simulations of clathrate hydrates.
With this information gathered in one place, it will be a valuable resource for both
experienced researchers, and researchers and graduate students of science and
engineering just starting their studies of these fascinating substances. The authors
have aimed at making each chapter as comprehensive as possible, but in a work of
this scope, valuable work will inevitably not be discussed.
A summary of the chapter contents follows.
Chapter 1 reports the major highlights in the development of clathrate hydrate
knowledge and then highlights contributions of the National Research Council of
Canada group where the authors of this volume have worked or which they were in
close collaboration.
xiv Preface

Chapter 2 gives a more detailed historical outline of the study of clathrate hydrates
from the classical period up to 1970 when the hydrate crystallographic structure
became known and the statistical mechanical model of clathrate hydrates was
developed. We surveyed some of the primary literature of this period to clarify some
of the historical aspects of these substances discovered by the early researchers.
Chapters 3 and 4 introduce the different hydrate cages made of hydrogen-bonded
water molecules and discuss the classification of clathrate hydrates as part of the
larger family of supramolecular compounds, and their techniques of synthesis,
respectively. Hydrates are presented as solid solutions with their stability being a
lattice property. Comprehensive tables are presented of the known guest molecules,
and summaries of their structural and physical properties are given in this chapter.
The different classes of clathrate hydrate phase equilibria are presented.
Chapters 5 and 6 discuss structural aspects of clathrate hydrates, semi-clathrates,
and salt hydrates. The importance of unconventional guest–host interactions
like hydrogen and halogen bonding is introduced. Different ways of looking at
hydrate structures based on layered structures and space filling cages using the
Frank–Kasper approach are presented, and related non-hydrate clathrates are
introduced.
Chapter 7 introduces thermodynamics and statistical mechanics of clathrate
hydrates with discussion of calorimetric methods and the van der Waals–Platteeuw
theory and some of its extensions. Many recent engineering applications and
extensions are not directly discussed as they are discussed in Chapter 16 or are
beyond the scope considered for this book. Tables of hydrate composition and
thermochemical information are presented.
Chapter 8 gives a summary of the application of molecular simulation methods
to study clathrate hydrate properties. Methods of characterizing structural and
dynamic properties of clathrate hydrates are discussed. Most of the emphasis is on
classical molecular dynamics and Monte Carlo results, but quantum mechanical
calculations of confinement effects for small molecules such as hydrogen and
methane in the clathrate hydrate cages are also reviewed. A table is given for
systems studied to date using molecular simulation methods.
Chapters 9, 10, 11, and 13 discuss X-ray and neutron diffraction and scattering,
general and specialized NMR methods and IR/Raman methods for studying
clathrate hydrates, respectively. The techniques are briefly introduced, and the
often complementary information they provide on clathrate hydrates are described.
The use of these methods in unraveling the structure and dynamics of guest–lattice
interactions is summarized.
Chapter 12 presents information, mainly from dielectrics and solid-state NMR, on
the molecular motion of guest and host molecules. The relationship between cage
geometry and guest dynamics is introduced, as is the effect of guest–host hydrogen
bonding on water molecule dynamics.
Chapter 14 presents the rate and mechanisms of hydrate formation and decom-
position from both macroscopic (process) and microscopic (mechanism) points of
view. Classical nucleation theory introduces a number of key parameters that are
pertinent to both homo- and heterogeneous nucleation mechanisms of hydrate
formation. Emphasis is placed on hydrate processes as phase changes occurring
 Preface xv

in the presence of mass and temperature gradients rather than chemical reactions
occurring in isotropic and isothermal systems. The various factors that modify
kinetics of hydrate formation are introduced and discussed from results gathered
from both experimental and molecular simulations. The hydrate memory effect and
possible mechanisms of kinetic hydrate inhibition (using both polymeric substances
and antifreeze proteins) are discussed in this chapter.
Chapter 15 deals with mechanical properties of clathrate hydrates, including
acoustic velocity, elastic constants, thermal expansion, and thermal conductivity.
Experimental and theoretical backgrounds for the study of these properties are
given. Some anomalous effects seen in the temperature dependence of the thermal
conductivity of hydrate phases, but absent in ice, are discussed in detail in this
chapter.
Chapter 16 presents with selected potential applications of clathrate hydrate com-
pounds, including flow assurance, natural gas recovery, desalination, concentration
of aqueous solutions, and the storage of natural gas, hydrogen, and gas separation.
This chapter is meant to be an overview of some applications, which will be well
studied in the near future.
The authors’ work described in this book has contributions from many colleagues,
staff, and students at the National Research Council of Canada who are named
in Chapter 1. The contributions of these individuals are gratefully acknowledged.
The work described would not have been possible without the material support of
the National Research Council of Canada from ∼1960 to 2011. As in any field, the
progress in clathrate hydrate research is the result of collaboration and contributions
from researchers in many countries. We hope to have given proper representation
of contributions from researchers from all parts of the world. We apologize for any
omissions, which are the result of the limited scope of some of the discussions in
this book.
We would like to acknowledge the contributions of Donald Davidson (1925–1986)
of the National Research Council of Canada as one of the pioneers in modern
hydrate research in Canada. Don (i) initiated a multi-technique approach to study-
ing gas hydrates; (ii) provided mentorship to generations of hydrate researchers
at the NRC; and (iii) wrote a number of monographs and book chapters, which
are exemplary for their clarity and are still useful today. At the time, the National
Research Council was a fertile multidisciplinary environment where cutting-edge
dielectric, NMR, single-crystal X-ray crystallographic, and simulation techniques
were being developed, and almost immediately being used in understanding these
substances. After Don’s passing, this tradition was maintained at the NRC.
The editors would like to thank the authors of the chapters in this book for their
contributions and their patience with our numerous requests for editorial changes.
We would particularly like to thank Christopher I. Ratcliffe, Amadeu K. Sum, Peter
Englezos, and Dennis D. Klug who also commented extensively on chapters other
than their own.
We would like to thank our wives Beth and Dorothy for support and dealing with
the seemingly unending demands on our time while we worked on this book. We
thankfully acknowledge their indirect, but important contributions in getting this
book project completed.
 1

An Introduction to Clathrate Hydrate Science

John A. Ripmeester 1 , Saman Alavi 1,2 , and Christopher I. Ratcliffe 1
1
National Research Council of Canada, 100 Sussex Drive, Ottawa, ON, K1A 0R6, Canada
2
University of Ottawa, Department of Chemistry and Biomolecular Science, STEM Complex, 150
Louis-Pasteur Pvt., Ottawa, ON, K1N 6N5, Canada

1.1 Introduction
The first intersection of clathrate hydrates and human endeavor took place in the late
1700s. A number of researchers (natural philosophers) working on the solubility of
newly discovered airs (gases) observed unexpected ice-like solids formed above the
freezing point of ice when certain gases were passed into cold water or when such
a solution was frozen. Davy identified these solids as two-component water–gas
compounds and named them “gas hydrates.” After some 140 years and much
research, these solids were shown to be clathrates, materials where small molecules
(guests) are trapped in an ice-like lattice (host) consisting of hydrogen-bonded
water cages. During the time between initial discovery and final identification, gas
hydrates confounded researchers by having a number of properties that countered
concepts derived from mainstream chemistry. For instance, the hydrates were
non-stoichiometric, the water-to-gas ratios were not small whole numbers, and they
decomposed upon heating or depressurization to give back the unchanged starting
materials. The lack of chemical bonds between the water and the gas in the hydrates
suggested that these were not real chemical compounds and in fact were the first
examples of “chemistry beyond the molecule” – supramolecular compounds.
From phase equilibrium studies, we now know that when many gases and water
are in contact under appropriate pressure (P) and temperature (T) conditions, a solid
hydrate will form. The gas hydrates store gases, including natural gas, very efficiently
with one volume of solid hydrate storing some 160 volumes of gas at standard tem-
perature and pressure (STP). Since a number of gas hydrates are found naturally, this
class of materials can be taken to be an unusual type of mineral. There are many sites
in the geosphere where natural gas and water are in contact under the conditions
required to form gas hydrate. Locations where this occurs are in sediments offshore
of continental margins, under permafrost, and in some deep freshwater lakes.
Well before the discovery of natural gas hydrate in the geosphere, oil and gas
engineers encountered blocked natural gas pipelines during cold weather operation
Clathrate Hydrates: Molecular Science and Characterization, First Edition.
Edited by John A. Ripmeester and Saman Alavi.
© 2022 WILEY-VCH GmbH. Published 2022 by WILEY-VCH GmbH.
2 1 An Introduction to Clathrate Hydrate Science

which was initially attributed to ice formation from moisture in wet gas. Knowledge
of earlier work on solid methane hydrate led Hammerschmidt in the 1930s to the cor-
rect explanation for the pipeline blocks – they were made of solid methane hydrate
rather than ice. Since then, during the exploration, production and transport phases
of hydrocarbon resources, blockage by natural gas hydrate formation has become a
well-known hazard, resulting in possible serious damage and loss of life, for example
in the Deepwater Horizon oil spill of 2010. Much research has been carried out
to prevent or manage hydrate formation in pipelines. Other problems related to
gas hydrates have been identified, including marine geohazards, such as submarine
landslides, and sudden gas releases from hydrate formations.
Because of the vast amounts of trapped natural gas in hydrate form globally,
gas hydrates have been evaluated to be a significant unconventional natural gas
resource. Hydrate deposits have been mapped in many locations around the world,
usually using geotechnical methods that depend on the location of unexpected
solid hydrate–liquid water interfaces which act as seismic reflectors. Test wells for
gas production have been drilled in the Mackenzie Delta, Canada (Mallik 2L38),
Alaska, the Nankai trough offshore Japan, and offshore China. Many problems
have been encountered in producing gas from hydrate reservoirs, including the
development of the best techniques for destabilizing the solid hydrate and captur-
ing the resulting gas. Some hydrate deposits, often associated with hydrocarbon
seeps or vents, exist as outcrops on the seafloor. Whereas most of the methane
in hydrate reservoirs is of biogenic origin, hydrates associated with seeps or hot
vents are formed from thermally altered hydrocarbons originally residing in deeper
reservoirs. Some hydrate outcrops are home to specialized biological ecosystems
where microbes feed on hydrocarbons and these in turn become a food source for
“ice-worms.”
Besides the marine and terrestrial natural gas hydrates, there are gas hydrates of
air (mainly N2 and O2 ) deep inside glaciers. The hydrate zone starts at pressures
where gas bubbles in the ice disappear. There has been much speculation regarding
the existence of hydrates in extra-terrestrial space, that is, on Mars, Titan, Enceladus,
and the heads of comets. One of the best candidates for finding such a hydrate would
appear to be that of CO2 . Although lots of spectroscopic data exist for free solid
CO2 and ice in extra-terrestrial space, no sign of CO2 hydrate has been found, see
Chapters 3 and 13 for possible reasons.
The large gas capacity and water as cheap working fluid make gas hydrates
interesting materials for industrial applications. Gas hydrates are generally selective
for guest molecule adsorption which allows the separation of gas mixtures. Much
as salt is excluded when brine is frozen in desalination processes, gas hydrates have
the same ability, but now the properties of the solid phase can be adjusted. For
example, depending on the choice of guest, the hydrate freezing point can be well
above the ice point, so saving on refrigeration costs. The same principle applies
to cool energy storage where the freezing point of the hydrate can be tuned to
minimize operational costs. Further applications include dewatering of fruit juices,
 1.1 Introduction 3

sewage sludge and wood pulp, and the storage of unstable molecules such as ozone
and chlorine dioxide. A more exotic application was the separation of radioactive
radon gas from a gas mixture.
The gentler conditions required for the formation and storage of methane in
solid hydrate form as compared to the low temperature required for liquid nitrogen
storage of liquefied methane has resulted in the evaluation of transport by these two
means. Indeed, some cost advantages become apparent for solid hydrate transport
if methane has to be transported from stray fields where construction of a liquid
natural gas (LNG) plant is not cost effective. Other applications for storage have
been explored, e.g. for hydrogen as fuel gas and CO2 for greenhouse gas separation
and storage.
Gas hydrates, because of their unique properties, have demonstrated some enter-
tainment value. The “burning snowball” results when methane from decomposing
methane hydrate is ignited and this phenomenon has been admired by many,
both live and in print. In the early 1980s, it was proposed that sudden, massive
decomposition of marine methane hydrates could be the cause of disappearances
of ships and planes in mythically mysterious areas such as the Bermuda triangle.
It appears the mystery novel “Death by gas hydrate” still needs to be written:
hydrates have great potential as difficult to track murder weapons. The media also
have frequently given news coverage of “burning ice” which is rediscovered every
10 years or so.
From the earlier examples, it is clear that gas hydrates are interesting and unusual
materials partly because nature makes them and partly because there are many
potential uses which unfortunately remain largely prospective. This book will
emphasize the molecular chemical, physical, and material aspects of clathrate
hydrates, that is, the many details needed to understand the macroscopic properties
and processes mentioned earlier. Engineering and geological aspects of the gas
hydrates have been covered admirably in a number of previous books mentioned
later.
In Section 1.2 of this chapter, we highlight milestones of clathrate hydrate science
up to the present. The history and context of some of these earlier developments
are discussed in greater detail in Chapter 2 and in chapters that follow and the
relevant references can be found there. From their beginning and in the decades
that followed, many centers of clathrate hydrate research emerged in different
parts of the world. From the early 1960s with the work of Don Davidson and
coworkers, the National Research Council (NRC) of Canada in Ottawa emerged as
one of the active centers of research in this field. In Section 1.3, we give a summary
of the contributions to clathrate hydrate science made in the NRC of Canada
during this time period. Contributors to the clathrate hydrate research at the NRC
are acknowledged in Section 1.4. Some influential books and review articles on
clathrate hydrates that appeared during this period and up to the current time are
introduced in Section 1.5. International conferences focusing on clathrate hydrate
science are listed in Section 1.6.
4 1 An Introduction to Clathrate Hydrate Science

1.2 Selected Highlights of Clathrate Hydrate Science

Research Up to the Present

In this section, we summarize selected highlights of clathrate hydrate research,

emphasizing contributions to molecular science. Not all engineering and geological
discoveries are covered in detail in this selection. Full author names and references
for most of these highlights are given in the following chapters.

1810 Sir Humphrey Davy correctly identified a solid material, previously thought
to be solid chlorine, as a compound of chlorine and water and called it “gas
hydrate.”
1823 Faraday determined the composition of chlorine hydrate to be Cl2 ⋅10H2 O.
1823 Faraday acting upon a suggestion by Davy, used decomposition of gas
hydrates in confined vessels as a method of liquefying gases.
1828 Löwig prepared bromine hydrate and determined the formula Br2 ⋅10H2 O for
the compound.
1829 de la Rive prepared SO2 hydrate, SO2 ⋅14H2 O, and proposed that all common
gases form hydrates.
1840 Wöhler prepared H2 S hydrate.
1843 Millon prepared chlorine dioxide hydrate, the first example of the
preservation of an unstable chemical species, ClO2 , an explosive-free radical.
1852 Loir prepared solid binary hydrates from water, H2 S, or H2 Se and
halogenated hydrocarbons like chloroform, their composition remained
unknown for some 30 years.
1856 Berthelot prepared the first pure hydrates of organic compounds, namely,
those of methyl chloride and methyl bromide. He also claimed that CS2
formed a hydrate, starting a controversy about its existence that lasted 40
years.
1863 Wurtz prepared ethylene oxide (EO) hydrate, the first example of a
water-soluble guest. Its composition and melting point diagram were not
determined until 1922.
1878 Isambard showed that the equilibrium pressure of chlorine hydrate is
univariant.
1878 Cailletet designed and built apparatus suitable for working at high pressure
and low temperature. This was of great value for the preparation of new gas
hydrates and the determination of phase equilibria. He illustrated this by
preparing new hydrates of acetylene and phosphine.
1882 Wróblewski prepared CO2 hydrate.
1882 de Forcrand prepared and characterized 33 double hydrates of H2 S with a
variety of guests and established similarities of composition, M⋅2H2 S⋅23H2 O.
Studies were extended to double hydrates with H2 Se as well as a simple
hydrate of H2 Se.
1882 Cailletet and Bordet showed that mixed hydrates of CO2 and PH3 were not
simply physical mixtures of simple CO2 and PH3 hydrates but hydrates with
unique properties.
1883 de Forcrand applied calorimetry to gas hydrates and assigned most of the
thermal effects to the dominant presence of water in the hydrate.
Another random document with
no related content on Scribd:
The Project Gutenberg eBook of Kansallisia
lauluja
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.

Title: Kansallisia lauluja

Author: Lauri Soini

Release date: September 7, 2023 [eBook #71582]

Language: Finnish

Original publication: Porvoo: Werner Söderström, 1900

Credits: Tapio Riikonen

*** START OF THE PROJECT GUTENBERG EBOOK

KANSALLISIA LAULUJA ***
KANSALLISIA LAULUJA

Kirj.

Lauri Soini

Porvoossa, Werner Söderström, 1900.

SISÄLLYS.

Suomen laulu.
Suomen kielellä.
Suomen lippu.
Suomettaren laulu.
Elä sure, Suomeni!
Karjala apua huutaa!
Siirtolaisille.
Suomen pojat.
Tuuloselle.
Iloisin mielin.
Rauhan sankari.
Kumpumäen vanhukset.
Herra sensori.
Ihanteen etsijä.
Torpan poika.
Pohjolan neidet lännessä.
Kotkankallio.
Keväinen kotiutuminen.
Iltakello.
Ilta.
Neitosen sulhaset.
Neitokolmikko.
Neitonen, tietäjä kuitenkin.
Annikki.
Kumma tyttö.
Koulu jo alkaa!
Valkamalle.
Elämä ja ihanteet.
Täyteläs rinta.
Nuoret, nuoret.
Konsahan!
Keväiset yöt.
Tuoksuva tuomen oksa.
Kultani kartano.
Pihlajan juurella.
Hänen luonansa.
Kuusi on tumma ja koivu on seljäs.
Lemmenpaula.
Ei toki semmoista tehdä saa!
Tule kultani keinuhun!
Sydämillä leikkimistä.
Minä ja hän.
Juhannus ja joulu.
Taivaan pilvet.
Sinä olet päivyt.
Sinä olet päivä ja minä olen kuu.
Ruusun kukka ja vaahteran oksa.
Kukkaset ja kukkasvarkaat.
Jänis ja — kultani.
Niin täytyy.
Kullan haudalla.
Surujeni lampi.
Suuren surun keskelläkin.
Luottava vuottaja.
Minä olen sellainen.
Raitis Rautiainen.
Päiväläisen mietteitä.
Kulkijapoika.
Hulivilipoika.
Vaikeassa asemassa.
Mitäpä noista —!
Kuohuvan kosken kunnaalla.
Lintu lenti oksalle huojuvalle.
Laulaja- ja tanssijatyttö.
Pikkunen tyttö.
Kultaansa ihaileva.
Järvellä.
Meripojan morsian.
Kullastansa jäänyt.
Salainen lempi.
Illalla ja aamulla.
Lempi.
Suomen laulu.

Solahda, Suomen laulu, sointuvasti, helähdä helkkyvästi

kaikumaan, soi meille suruissakin toivoisasti, soi vastuksissa
voima versomaan!

Hajota meistä hennot huolten hunnut,

terästä tarmokkuutta jänteriin,
luo tunteihimme vakuutuksen tunnut
ja vahvistusta töihin ponteviin!

Kuin tammen juuret maamme tanterille

syvennä sydämiimme oikeus —
kuin päivän säihkyt lammen lainehille
sytytä rintoihimme rakkaus!

Julista ilo kansan valtikaksi,

herätä meihin henki veljeyden,
se kansassamme nosta johtajaksi
jokaisen aatosten ja toimien!

Soi, Suomen laulu, nuorten kantelilla

tuhansin uhkuäänin helkkyen,
soi kaikkialla maamme kunnahilla
ihana enne aamun henkisen!

Solahda, Suomen laulu, sointuvasti, helähdä helkkyvästi

kaikumaan, soi meille suruissakin toivoisasti, soi vastuksissa
voima versomaan!

Talvella 1899.
Suomen kielellä.

Suomen kielellä Suomen lapsi "äiti" ensin sanoo, Suomen

kielellä äidiltänsä tarpeitansa anoo.

Suomen kielellä Suomen lapsi

alkaa aakkosista,
täyttää henkensä suomalaisen
tiedon aartehista.

Suomen kielellä toisillemme

tunteet tulkitsemme,
vanhat muistot ja matkan määrät,
uskot, aattehemme.

Suomen kielellä suomalainen

lakejansa laatii,
Suomen kielelle oikeutensa
vierahilta vaatii.

Suomen kielellä muilta mailta

aatevirrat tuomme,
Suomen kielellä hengen helmet
maailmalle luomme.

Suomen kieli on piennuutemme, suuruutemme kehto,

Suomen kieli on suomalaisen hengen elinehto.

1899.

Suomen lippu.
 Liehu, liehu korkealla lippu sinivalkonen! Laula, kansa, lipun
alla laulu toivon, vapauden!

Liehu taivon siinnokkuutta

vetten vöistä heijastain,
pohjan hangen puhtoisuutta
henkehemme heijastain!

Hengen voimin toimikamme eestä maamme vapauden!

Liehu, lippu, toivojamme liehu ylle ilmojen!

1896—99.

Suomettaren laulu.

Soitin kerran kanteletta taaton tanhuilla, jossa leikki

siskosarja kukkakunnahilla.

Riemukasta, onnekasta
oli meillä silloin,
Väinämöisen laulujansa
laulaessa illoin.

Tuli vieras kaukomailta

kotikullan ryösti,
veikot siskot säälimättä
sorron alle syösti.

Täällä nyt mä kaihomielin

pellavasta kitken,
pellavasta kitkiessä
vaivojani itken.

Kuivu, kuivu kyyneleeni, kuivu silmäkulta, kyllä vielä

valkeneepi murheyöni multa!

1896—1899.

Elä sure, Suomeni!

Elä sure, Suomeni, mitä olet ollut, se ei ole matkasi määrä.

Siinä ei suvi ole missä on pälvi — semmoinen usko on väärä.

Elä sure, Suomeni, mitä olet ollut,

sitä elä jarruksi laita.
Menneestä hetkelle pystytä pohja,
tulevalle viljele maita.

Raivaos salosi sä päivyen paistaa,

päivä sun hankesi hiutaa,
kumpusi kaunosin kukkasin kietoo,
viihtäen lastesi liutaa.

Vanhojen varjossa kasvavat lapset,

nuoret ne toimissa varttuu.
Koko kansa kilvalla työssä kun häärää,
laajoiksi viljeemme karttuu.

Suomeni, muheaksi peltosi kynnä,

kylväös siemen parhain,
niin sinun viljasi kaunona kasvaa,
kuuluna maailman tarhain.

Vieras jos viljasi tahtoisi viedä,

valppaana vahdi ja estä,
vaan jos se vie, niin kylväissä uutta
jäykkänä, jäyhänä kestä.

Suomeni, kansani, et voi kuolla, jos sinä tahdot elää, jos

sinun henkesi hervahtamatta elämän sointuja helää.

1899.

Karjala apua huuiaa!

Suomeni kallis, kaunoinen, kansa suurien toivetten,

kukkiva, kasvava kansa! Käännä kasvosi Karjalaan, kuule,
vartiopaikallaan Karjala apua huutaa!

Suomeni, sorjana kumpuna

nouset suon sinä helmasta,
Karjala luoksesi nosta!
Peltosi laajeten paltoaa,
hengenlaihosi aaltoaa —
Karjalan kannel sammuu!

Suomeni riennä joutuisaan

Karjalan heimoa auttamaan,
veljesi luoksesi nosta!
Hengen salamat sinnekin
lyökööt valkeutta rintoihin
velttona nukkuvan heimon!

Karjala, suoja Suomemme, nouse jo yhteistaistolle, valolla

voittosi voita! Päivän kaarena nouse sä, valkase pilven
lievettä, Suomen suojana seiso!

Jalovaaralla 1897.

Siirtolaisille.

Hellanlettu, kun kallis nahka on noilla muutamilla! Eivät he

usko säilyvänsä maansa tanterilla.

Menkää, menkäätte herrantertut,

säilyttäkää päänne!
Pois kun puikkivi aikanansa,
oi, se on viisas käänne!

Saammeko kunnian kutsua teitä

viisahimmiksi maamme,
vai ehkä sankariseppeleillä
somistella saamme?

Suokaa joskus muistelu meille tomppelijoukollekin, että me

elämme Suomellemme, sille kuolemmekin.

1899.
Suomen pojat.

Suomen poikia keisari aikoo viedä Venäjälle. Siellä ne

joutuisi suomalaiset oudolle elämälle.

Suomen pojat jos Venäjälle

vietäisi virmakan soittoon,
itkien nousisi Suomen immet
pilvisen päivän koittoon.

Suomen pojat jos Venäjällä

venäjänlimppua söisi,
eivät ne silloin Suomen pellot
hempeinä heilimöisi.

Suomen pojat jos Venäjällä

sortuisi suureen vaivaan,
Suomesta armas keisari saisi
tyhjän maan ja taivaan.

Elkää itkekö Suomen immet tokkopa surkua liekään,

tokkohan keisari Suomen poikia Venäjälle viekään.

1899.

Tuuloselle.

Aaltojen kehdot keinuavat, vihreät lehdot liplattavat, tuuli

kun kiitää ympäri maan, lännestä liitää Kalevalaan.
 Tuulonen lännen, lennellä saat sinne ja tänne Kalevan
maat. Kaikota häivän hiuteet pois, ettei ne päivän peittona ois!

Lentävä tuuli, suutele sä lempein huulin itkevätä! Rannoilta

Suomen pois sumu vie, valkase huomen, selvitä tie!

1899.

Iloisin mielin.

Murheet me heitämme heikommille, ilo toki tulkoon myötä!

Iloisin mielin me soutelemme, vaikk' on se vahvaa työtä.

Kaakkoistuulessa aallot lyövät

pienen purtemme laitaa,
vaan kun me vahvasti soutelemme,
minkä ne meille taitaa.

Iloisin mielin me soutelemme, vaikkakin myrsky kantaa,

purtemme keinuu myrskyn halki kohden toivon rantaa.

1899.

Rauhansankari.

I.

Hän raikkaan kainona ilmestyi kuin soinnahdus

paimensäkeen. Oli temmattu armaasta laaksostaan ja tuotuna
sotaväkeen.

Hän seisoi sarjassa sankarien

kuin korvessa koivas sorja.
Hänen mielensä pulppusi nuoruuttaan
kuin lähde ja sen puro norja.

Hän sai heti huomion päällystön,

ivan piikit ja iskut ja ilkat.
Sotaveikkojen sai hän vehkeilyt,
tulotemput ja lyönnit ja pilkat.

Kun niin häntä ilkkuen pilkattiin,

hän tyynenä kaiken kesti,
vaan joskus vienolla hymyllään
rajut leikit hän hälvensi, esti.

Vaan muita kun syyttä sorrettiin,

hän katsoi lyötyä silmiin,
ja silloin kainossa katseessaan
tuli kärsivä lempeys ilmiin.

Hän tyynenä täytteli tehtäviään

ja päästyä toimistansa
ei tyttöjä, viiniä etsinyt hän,
vaan aatteli aatteitansa.

Useasti hän illoin yksikseen

ulos rannalle lahden astui.
Useasti kun katseli hän yli veen,
suli silmä ja kyynelin kastui.
 Kotilaaksoonsa liiti hän aatoksin
luo tuttujen, rakkaimpainsa,
koko kansankin armaan synnyinmaan
näki ummuissa unelmainsa.

Näki vielä hän umpujen aukenevan,

näki kärsivän kansansa kerran
ajan uuden auvossa astelevan
valon välkyssä taivaan Herran.

Hänen henkensä täyttäisi ihmisten

elonvoimaa uhkuvat rinnat,
ja voima hengen ja veljeyden
lois heikoille suojeluslinnat.

Ois aika se onnen ja oikeuden.

Työn onni se onnena oisi.
Kukin työssä kuntonsa näyttäisi
ja toistenkin toimia soisi.

Ja aika se aamuna koittava on

väkivallan ja sorron yöstä.
Oi, toittavat ruusut on vapauden
rakkauden ja rauhan työstä!

II.

Vaan viestejä outoja ilmestyi, koko kansan kautta ne liiti:

sotajoukkoja suuria vieraan maan kotikumpuja kohden kiiti.

Hän rannalla istui uinaillen,

unelmiinsa hän viestin kuuli.
Kuin nuoli se rintaan iskeytyi,
sydän synkkeni, vaaleni huuli.

Isänmaako on uhkaama sortajien,

isänmaako ja kansa sen kallis?
Sen joukkion polkea rakkaimpiaan
ikipäivinä hän ei sallis!

Hän niinkuin leimaus ukkosen

sitä vastaan lennättäisi!
Hän ennen sen löisi ja murskaisi
kuin tänne se ennättäisi! —

Vaan muistaen aatteensa armaimmat

syvemmälle hän sullousi pintaa.
Kuin kylmällä kouralla koskettain
nyt vihiäsi lämmintä rintaa.

— He eivätkö ihmisveljiä myös

ole juuresta suuremmasta?
Ja ihmistä puhdas ihmisyys
ei kielläkö surmaamasta?

Vaan kallista kansaamme surmaamaan

nuo ihmiset kulkevat tuolla.
Nyt pakko on surmata surmaajat
tai surmaajan nuolesta kuolla.

Siis rikkoa täytyvi ihmisyys,

ei välttää voi eikä estää.
Paremp' onkohan rikkoja olla nyt
vai rikkomus toisen kestää?
 Hän ristiin riipovin aatoksin
sitä selvitti tuskissansa.
Välin otsansa syvästi synkistyi,
välin vaaleni vuorostansa.

Vaan vihdoin puhtaana selvisi se kuin päivä mi usvista

herää. — Paremp' ihmisen ihmisnä kuolla on kuin
ihmissyöjänä elää.

III.

Rajaseudulla palteet pilvytten loi synkkiä varjoja vesiin.

Rajaseudulla sankarit vartosivat mikä turmio tulleekin esiin.

Isänmaatansa sinne suojaamaan

oli kulkenut uljas kansa,
ja se välkytti kirkkaita kalpojaan
vihamiehiä vuottaissansa.

Ja torvet ja rummut ne raikuivat

ja kummut ne kaikui vastaan,
sotajoukot kun saapuivat mahtavat
ja kuuluisat kuljennastaan.

Kodin vapaus — vallan tavoitus

veti joukkoja vastatuksin.
Tuliluikut tykkien, kanuunain
ne ammotti suutasuksin.

Vaan aivan alkaissa ammunnan

mies nuorekas joukosta nousi,
ja kun vallille asteli yksin hän,
hänen tukkansa tuulessa sousi.

Kuin kuusi min latvasta usvaa pois

on pyyhkinyt aamun loiste,
niin seisoi harjalla vallin hän,
sinisilmissä päivän toiste.

Ylös nosti hän päivässä päilyvän pään,

jota viillytti vilpas tuuli.
Sotajoukko se ylhäältä soinnahtavan
hymynhenkevän kuiskeen kuuli.

Isänmaatani armasta vastaan te

vihan kaunaa tahdotte kantaa.
Minä lempeni, työni ja henkenikin
isänmaalleni tahdon antaa.

Sen rannalla seison ja ruumiini

yli kulkien saatte sen voittaa.
Minut ampua saatte jos tahdotte,
teit' en tahdo vahingoittaa. —

Pian alkoi paukkua kanuunat.

Sota rauhansankarin kaatoi.
Ja joukkoa maansa puoltajain
vihamiehet mahtavat raatoi.

Heinäkuulla 1899.

Kumpumäen vanhukset.