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 NATO Science for Peace and Security Series - A:
Chemistry and Biology

Engineering
Crystallography: From
Molecule to
Crystal to Functional Form

Edited by
Kevin J. Roberts
Robert Docherty
Rui Tamura

AB 3
Engineering Crystallography: From Molecule
to Crystal to Functional Form
NATO Science for Peace and Security Series
This Series presents the results of scientific meetings supported under the NATO
Programme: Science for Peace and Security (SPS).

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Following a transformation of the programme in 2006, the Series has been re-named and
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Series A: Chemistry and Biology

Engineering Crystallography: From
Molecule to Crystal to Functional
Form

edited by

Kevin J. Roberts
School of Chemical & Process Engineering
University of Leeds
Leeds, United Kingdom

Robert Docherty
Pfizer Global R&D
Pharmaceutical Sciences, Pfizer Global R&D
Sandwich, Kent, United Kingdom

and

Rui Tamura
Graduate School of Human and Environmental Studies
Kyoto University
Sakyo-ku, Kyoto, Japan

Published in Cooperation with NATO Emerging Security Challenges Division

Proceedings of the NATO Advanced Study Institute on Molecules
to Crystals to Powders: Understanding Structure Versus Function
Erice, Sicily, Italy
4–14 June 2015

Library of Congress Control Number: 2017944199

ISBN 978-94-024-1118-8 (PB)

ISBN 978-94-024-1115-7 (HB)
ISBN 978-94-024-1117-1 (eBook)
DOI 10.1007/978-94-024-1117-1

Published by Springer,
P.O. Box 17, 3300 AA Dordrecht, The Netherlands.

www.springer.com

Printed on acid-free paper

All Rights Reserved

© Springer Science+Business Media B.V. 2017
This work is subject to copyright. All rights are reserved by the Publisher, whether the
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with respect to the material contained herein or for any errors or omissions that may
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published maps and institutional affiliations.
Scientific Programme Committee
Christer Aaker€
oy (Kansas State University, USA)
Gerard Coquerel (University of Rouen Normandy, Rouen, France)
Robert Docherty (Pfizer Worldwide R&D, UK)
Kevin J. Roberts (University of Leeds, UK)
Rui Tamura (Kyoto University, Japan)

Organising Committee
Robert Docherty (Pfizer Worldwide R&D, UK)
Annalisa Guerri (University of Florence, Italy)
Kevin J. Roberts (University of Leeds, UK)
Paola Spadon (University of Padova, Italy)
Giovanna Scapin (Merck & Co., Inc., NJ, USA)
Preface

This book is formed from selected papers and tutorials on the theme of Engineering
Crystallography: From Molecule to Crystal to Functional Form which were
presented at the 2015 International School of Crystallography. These international
summer schools are renowned for bringing together scientific experts in various
crystallographic fields with motivated students from around the world in an infor-
mal but engaged atmosphere. This facilitates a high level of interaction and
discussion which allows the subject matter experts present to help shape the next
generation of academic and industrial talent in the discipline. This was the 48th
such event which was held at the Ettore Majorana Foundation and Centre for
Scientific Culture in the beautiful and historic hilltop town of Erice in Sicily.
Lecturers were chosen from world experts in the fields of crystallography, solid-
state chemistry, crystallisation, materials science, computational multi-scale
modelling as well as particle technology and surface characterisation. Structural
and modelling techniques were integrated throughout the summer school. This
allowed participants to envisage how, in the next few years, computational and
experimental workflows will be seamlessly integrated during the transition from
molecule to crystal to function. The course consisted of plenary lectures, talks
selected from poster abstracts and technologies, plus, on the final day, a facilitated
question and answer session with a selected panel from the invited speakers.
Our motivation in designing the summer school was to help build bridges
between the solid-state architecture, the landscape of particle and surface properties
accessible from this structure and the impact of these on the function and perfor-
mance of structured products. This intent is inherent in the design of this book
where we have assembled the component chapters into:
• Form (inherent physical and chemical properties)
• Formation (how to prepare)
• Function (properties and performance)
Our construct of the course and the book has been shaped by a scientific
storyboard created by our community over the last few decades. These include:

vii
viii Preface

• The key concept of the crystal as a supramolecular assembly [1]

• Crystal engineering – the design of functional organic solids [2, 3]
• The pioneering work on stereochemical control and manipulation of nucleation
and crystal growth [4]
• Towards knowledge-based approaches to crystal design [5]
• A structural perspective on the morphology and surface chemistry of molecular
materials [6, 7]
• Pharmaceutical materials sciences and the materials science tetrahedron [8, 9]
The integration of this storyboard within our book is very timely, and the themes
captured remain very contemporary. This is exemplified with recent conferences
including the International Workshop on the Crystal Growth of Organic Materials
(CGOM) [10]; Molecules, Materials and Medicines (M3) [11]; as well as the
funding of the cross-sector ADDoPT (Advanced Digital Design of Pharmaceutical
Therapeutics) initiative [12] in the UK. Global engagement in the area remains high
with the Novartis-MIT Center for Continuous Manufacturing [13] and the Center
for Structured Organic Particulate System [14] in the USA, the Synthesis and Solid
State Pharmaceutical Centre (SSPC) in Ireland [15] as well as the Centre for
Innovative Manufacturing in Continuous Manufacturing and Crystallisation
(CMAC) in Scotland [16] reflecting the fusion of crystal design, particle engineer-
ing and innovative manufacturing paradigms.

Leeds, UK Kevin Roberts

Sandwich, Kent, UK Robert Docherty
Sakyo-ku, Kyoto, Japan Rui Tamura
March 2017

References

1. Desiraju GR (1997) The crystal as a supramolecular entity. Wiley, Chichester

2. Desiraju GR (1989) Crystal engineering: the design of organic solids. Elsevier, Amsterdam
3. Seddon KR, Zarawotko M (1999) Crystal engineering: the design and application of functional
solids. NATO ASI Series, vol 539
4. Weissbuch I, Lahav M, Leiserowitz L (2003) Towards stereochemical control, monitoring, and
understanding of crystal nucleation. Crystal Growth Des 3:125–150
5. Allen FH et al. (2006) Knowledge based approaches to crystal design. Cryst Eng Commun 8:11
6. Clydesdale G, Roberts KJ, Walker EM (1996) The crystal habit of molecular materials:
a structural perspective, In: Gavezzotti A (ed) Molecular solid state: syntheses, structure,
reactions, applications, vol 2. Theoretical aspects and computer modelling, chapter 7,
pp. 203–232
7. Roberts KJ, Hammond RB, Ramachandran V, Docherty R (2016) Synthonic engineering: from
molecular and crystallographic structure to the rational design of pharmaceutical solid dosage
forms. In: Abramov YA (ed) Computational approaches in pharmaceutical solid state chem-
istry, ISBN 9781118700747, Copyright © 2016 Wiley, Inc.
Preface ix

8. Hancock BH, Elliot J (2006) Pharmaceutical materials science: an active new frontier in
materials research. MRS Bull 31:869
9. Sun CC (2009) Materials science tetrahedron – a useful tool for pharmaceutical research and
development. J Pharm Sci 98:1671–1687
10. http://www.crystalgrowth2016.co.uk/ and http://pubs.acs.org/page/cgdefu/vi/11.html
11. Almarsson O, Vadas EB (2015) Molecules, materials, medicines (M3): linking molecules to
medicines through pharmaceutical material science. Crystal Growth Des 15(12):5645–5647
12. https://www.addopt.org/
13. https://novartis-mit.mit.edu/
14. http://www.csops.org/
15. http://www.sspc.ie/
16. https://www.cmac.ac.uk/
Acknowledgements

The majority of the organisational efforts that were so vital to the success of the
course were championed by Annalisa Guerri and Paola Spadon. They secured the
majority of the funding and co-ordinated the participant selection process in a
highly diligent and professional manner. In partnership with the orange scarves
team (Giovanna Scapin, Valentina Marcheselli, Vania André, Paolo Mazzeo,
Matteo Lusi, Tamlyn Young, Francesco Farinella and Martin Schmidt), Annalisa
and Paola created a warm welcoming atmosphere where students could engage with
each other and with the invited subject matter experts. The red team Erin Davis,
Fred Boyle and Fabio Nicoli played a crucial role providing audiovisual support for
the lectures as well as the computing infrastructure for the tutorials. The scientific
and organising committees gratefully acknowledge all of the Ettore Majorana
Centre staff for their support during the event.
The editors would like to thank Ulrike Aufderhorst for directing and organising
the editing of the Erice summer school proceedings and for her energetic support
regarding assembling this book for publication. We would also like to thank Mauris
Chen and Hayley Harding for their help.
The summer school was financed by NATO, and we gratefully acknowledge the
NATO Science Committee for their continued support. Generous financial support
was also received from the International Union of Crystallography, the European
Crystallographic Association, the Cambridge Crystallographic Data Centre, Merck,
AbbVie, Dectris, PANalytical and New York University.
The development, delivery and publication of this summer school proceeding
represent a deliverable of the Advanced Digital Design of Pharmaceutical Thera-
peutics (ADDoPT) research project funding through the UK’s AMSCI scheme, and
we gratefully acknowledge them for their generous support.

xi
xii Acknowledgements
Contents

Part I Form
1 Crystal Science Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Vasuki Ramachandran, Peter J. Halfpenny, and Kevin J. Roberts
2 Molecular Structure and Chirality and Chiral Crystals . . . . . . . 21
Reiko Kuroda
3 Supramolecular Assembly and Solid State Chemistry . . . . . . . . . 35
Christer B. Aaker€oy and Manomi D. Perera
4 Solid Form Landscape and Design of Physical Properties . . . . . . 45
Christer B. Aaker€oy and Bhupinder Sandhu
5 Design of Physical Properties and Solid Form Design . . . . . . . . . 57
Robert Docherty and Kevin Back
6 Modelling Route Map: From Molecule Through the Solution
State to Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Robert B. Hammond
7 Crystal Growth and Morphology of Molecular Crystals . . . . . . . 109
Ian Rosbottom and Kevin J. Roberts
8 Determining Surface Energetics of Solid Surfaces . . . . . . . . . . . . 133
Jerry Y.Y. Heng
9 Crystal Effects Influencing the Course of Organic Solid State
Reactions: Perfect, Imperfect and Surface Effects . . . . . . . . . . . . 145
William Jones
10 Synthonic Engineering Modelling Tools for Product
and Process Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
Jonathan Pickering, Robert B. Hammond, Vasuki Ramachandran,
Majeed Soufian, and Kevin J. Roberts

xiii
xiv Contents

Part II Formation
11 Crystallisation Route Map . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
Diana M. Camacho Corzo, Cai Y. Ma, Vasuki Ramachandran,
Tariq Mahmud, and Kevin J. Roberts
12 Phase Diagrams for Process Design . . . . . . . . . . . . . . . . . . . . . . . 215
Gerard Coquerel
13 Seeding in Crystallisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Jose V. Parambil and Jerry Y.Y. Heng
14 Preparation, Stabilisation and Advantages of
Metastable Polymorphs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
Ana Kwokal
15 Crystallisation Control by Process Analytical Technology . . . . . 261
Ana Kwokal
16 Methods for Nano-Crystals Preparation . . . . . . . . . . . . . . . . . . . 275
Samir A. Kulkarni and Allan S. Myerson
17 Crystallization Control Approaches and Models . . . . . . . . . . . . . 289
Zoltan K. Nagy
18 Application of Ultrasound in Crystallization
(Sonocrystallization) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
Christopher J. Price
19 Continuous Pharmaceutical Crystallization from Solution . . . . . 315
Christopher J. Price
20 Viedma Ripening and Its Role in the Chiral Separation
of Optical Isomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
Martin Iggland, Giovanni Maria Maggioni, and Marco Mazzotti
21 Mechanochemistry and Its Role in Novel Crystal
Form Discovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
William Jones
22 Innovative Spontaneous Chiral Resolution Phenomenon:
Preferential Enrichment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
Rui Tamura

Part III Function

23 Pharmaceutical Solid-State Characterisation Techniques . . . . . . 367
Thomas D. Turner, Peter J. Halfpenny, and Kevin J. Roberts
24 Techniques for Crystal Optical Characterisation:
Chiroptical Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
Reiko Kuroda
Contents xv

25 Unique Ferromagnetic Properties Observed in All-Organic

Radical Liquid Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
Rui Tamura
26 Mechanical Deformation Chemistry of Crystals:
Designing Mechanical Performance . . . . . . . . . . . . . . . . . . . . . . 425
C. Malla Reddy
27 DEM Analysis of the Effects of Die Shape and Orientation
on Die Filling Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
Chunlei Pei and Chuan-Yu Wu
28 Finite Element Modeling of Powder Compaction . . . . . . . . . . . . 451
Alexander Krok and Chuan-Yu Wu
29 From Molecules to Crystals to Functional Form:
Science of Scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 463
Robert Docherty, Garry O’Connor, Radoslav Y. Penchev,
Jonathan Pickering, and Vasuki Ramachandran
Contributors

Christer B. Aaker€oy Department of Chemistry, Kansas State University,

Manhattan, KS, USA
Kevin Back Pharmaceutical Sciences, Pfizer Global R&D, Sandwich, Kent, UK
Diana M. Camacho Corzo School of Chemical and Process Engineering,
University of Leeds, Leeds, UK
Gerard Coquerel University of Rouen Normandy, Rouen, France
Robert Docherty Pharmaceutical Sciences, Pfizer Global R&D, Sandwich, Kent,
UK
Peter J. Halfpenny School of Chemical and Process Engineering, University of
Leeds, Leeds, UK
Robert B. Hammond School of Chemical and Process Engineering, University of
Leeds, Leeds, UK
Jerry Y. Y. Heng Department of Chemical Engineering, Imperial College
London, London, UK
Martin Iggland Institute of Process Engineering, Eidgen€ossische Technische
Hochschule Zurich, Zurich, Switzerland
William Jones Department of Chemistry, University of Cambridge, Cambridge,
UK
Alexander Krok Department of Chemical and Process Engineering, University of
Surrey, Guildford, Surrey, UK
Samir A. Kulkarni Novartis-MIT Center for Continuous Manufacturing and
Department of Chemical Engineering, Massachusetts Institute of Technology,
Cambridge, MA, USA
Reiko Kuroda Research Institute for Science and Technology, Tokyo University
of Science, Chiba, Japan
xvii
xviii Contributors

Ana Kwokal GlaxoSmithKline, R&D, Harlow, UK

Cai Y. Ma School of Chemical and Process Engineering, University of Leeds,
Leeds, UK
Giovanni Maria Maggioni Institute of Process Engineering, Eidgen€ossische
Technische Hochschule Zurich, Zurich, Switzerland
Marco Mazzotti Institute of Process Engineering, Eidgen€ossische Technische
Hochschule Zurich, Zurich, Switzerland
Allan S. Myerson Novartis-MIT Center for Continuous Manufacturing and
Department of Chemical Engineering, Massachusetts Institute of Technology,
Cambridge, MA, USA
Zoltan K. Nagy School of Chemical Engineering, Purdue University, West
Lafayette, IN, USA
Department of Chemical Engineering, Loughborough University, Loughborough,
UK
Garry O’Connor Pharmaceutical Sciences, Kent, UK
Jose V. Parambil Department of Chemical Engineering, Imperial College
London, London, UK
Chunlei Pei Department of Chemical and Process Engineering, University of
Surrey, Guildford, Surrey, UK
Radoslav Y. Penchev Pharmaceutical Sciences, Kent, UK
Manomi D. Perera Department of Chemistry, Kansas State University,
Manhattan, KS, USA
Jonathan Pickering School of Chemical and Process Engineering, University of
Leeds, Leeds, UK
Christopher J. Price Department of Chemical and Process Engineering,
University of Strathclyde, Glasgow, UK
Vasuki Ramachandran School of Chemical and Process Engineering, University
of Leeds, Leeds, UK
C. Malla Reddy Department of Chemical Sciences, Indian Institute of Science
Education and Research (IISER) Kolkata, Mohanpur, India
Kevin J. Roberts School of Chemical and Process Engineering, University of
Leeds, Leeds, UK
Ian Rosbottom School of Chemical and Process Engineering, University of
Leeds, Leeds, UK
Bhupinder Sandhu Department of Chemistry, Kansas State University,
Manhattan, KS, USA
Contributors xix

Majeed Soufian School of Chemical and Process Engineering, University of

Leeds, Leeds, UK
Rui Tamura Graduate School of Human and Environmental Studies, Kyoto
University, Sakyo-ku, Kyoto, Japan
Thomas D. Turner School of Chemical and Process Engineering, University of
Leeds, Leeds, UK
Chuan-Yu Wu Department of Chemical and Process Engineering, University of
Surrey, Guildford, Surrey, UK
About the Editors

Dr Kevin J. Roberts is the Brotherton Professor of

Chemical Engineering and currently directs the
EPSRC’s Centre for Doctoral Training in Complex
Particulate Products and Processes and the Centre for
the Digital Design of Drug Products at the University
of Leeds in the UK.
His research interests centre on crystallisation sci-
ence and engineering. This work encompasses both
fundamental and applied aspects with the latter being
directed towards the needs of the pharmaceuticals,
specialities, fine chemicals and nutritional product
sectors. Particular focus areas include solid-state
chemistry of molecular crystals; molecular and synthonic (intermolecular) model-
ling techniques; the use of synchrotron radiation techniques to probe condensed
interfaces in situ; the development and use of process analytical techniques (PATs)
for understanding, monitoring and controlling crystallisation processes; industrial
crystallisation processes and their scale-up from laboratory to manufacturing; and
the application of digital quality by design (dQbD) methodologies in the design and
production of high-added-value structured products.
Professor Roberts gained his degree and PhD in applied physics from Ports-
mouth Polytechnic, UK, before taking a post-doctoral research fellowship in
crystallisation and crystal characterisation at the University of Strathclyde,
UK. He subsequently held a Royal Society Fellowship at the Institute of Crystal-
lography at the Technical University of Aachen, Germany, before returning to the
UK to take up a faculty position in physical chemistry at the University of
Strathclyde. Later he was appointed as professor in chemical process engineering
and inaugural director of the Centre for Molecular and Interface Engineering at
Heriot-Watt University before moving to Leeds as head of chemical engineering
in 2000. There, he has been actively involved in setting up the Institute of
Particle Science and Engineering (IPSE) and the Institute of Process Research

xxi
xxii About the Editors

and Development (IPRD). He was awarded his DSc from the University of Strath-
clyde in 2004.
Over his career, he has published more than 250 peer-reviewed journal papers
and 7 chapters of books.

Dr Robert Docherty He is a senior research fellow

and head of materials sciences in drug product design
at Pfizer in Sandwich. His group is responsible for
solid form selection as well as materials and particle
characterisation. A key role of this group is the inte-
gration of drug substance attributes with drug product
design.
His research interests have focused on the structural
aspects of the assembly of molecules to crystals, crys-
tals to particles and particles to dosage forms. This
work encompasses both fundamental and applied
aspects of solid from design and particle engineering with the focus being directed
towards the journey of drug molecule to crystal to particle and product perfor-
mance. Specific areas covered include solid-state chemistry, molecular and mate-
rials modelling techniques and the use of state-of-the-art solid-state, particle and
surface characterisation techniques. All these combine to underpin an unprece-
dented structural perspective of the journey from molecule to medicine.
Dr Docherty gained his degree and PhD at the University of Strathclyde and joined
ICI/Zeneca in 1988 where he worked on the structure and crystallisation of dyes,
pigments, biocides, electrophotographic agents, agrochemicals and pharmaceuticals.
He joined Pfizer in 1999 as head of materials sciences. He holds a visiting profes-
sorship at the University of Leeds and is a fellow of the Royal Society of Chemistry.
Over his career, he has led, mentored and developed the research work of
numerous PhD and post-doctoral students at the industrial/academic interface and
published around 70 peer-reviewed journal papers and 6 chapters of books.

Dr Rui Tamura He is professor and councillor of the

Graduate School of Human and Environmental Studies
at Kyoto University in Japan and chairman of the
Division of Organic Crystals in the Chemical Society
of Japan.
His research fields cover synthetic and structural
organic chemistry, organic crystal and liquid crystal
chemistry and colloidal, magnetic and chiral chemis-
try. His current research interests focus on the discov-
ery of novel complexity phenomena occurring upon
the phase transition of organic crystals and in liquid
About the Editors xxiii

crystals under non-equilibrium conditions. It should be stressed that the observed

unusual phenomena cannot be reproduced in ordinary equilibrium systems. Thus
far, there are two phenomena found; “preferential enrichment” is a chiral
symmetry-breaking spontaneous enantiomeric resolution phenomenon observed
on recrystallisation of racemic crystals, while “magneto-LC effects” refer to the
generation of strong magnetic interactions induced by the application of low
magnetic fields in liquid crystalline phases of organic nitroxide radical compounds.
Professor Tamura gained his PhD in the Department of Chemistry, Faculty of
Science, Kyoto University, Japan, in 1980 and took two post-doctoral research
fellowships in the Department of Chemistry at Colorado State University (1980–
1982) and Princeton University (1982–1983), USA. He took up faculty positions in
chemistry at the National Defence Academy (1983), Ehime University (1988),
Hokkaido University (1995) and Kyoto University (1997) in Japan. In 2002, he
was appointed as professor at Kyoto University.
Over his career, he has published more than 160 peer-reviewed journal papers,
16 chapters of books and 7 Japanese patents.
Part I
Form
Chapter 1
Crystal Science Fundamentals

Vasuki Ramachandran, Peter J. Halfpenny, and Kevin J. Roberts

Abstract The fundamentals of crystal science notably crystallography, crystal

chemistry, crystal defects, crystal morphology and the surface chemistry of crystals
are introduced with particular emphasis on organic crystals.

Keywords Crystallography • Crystal lattices and systems • Crystal planes and

directions • Crystal defects • Crystal chemistry • Crystal morphology • Surface
chemistry

1.1 Introduction

Production of many crystalline products such as pharmaceuticals are underpinned

by a science-led quality by design (QbD) approach. This typically involves the need
to understand, predict, manipulate and control the core processes involved in drug
design, development and manufacture. The latter can be understood through a
consideration of an integrated 5F materials transformation pathway developed
from the target molecule’s molecular structure which links and interrelates:
• Formulae (atomic and molecular structure),
• Formation (crystallisation, precipitation, spray drying, etc.),
• Form (crystal size, morphology, polymorphic form, etc.),
• Formulation (blending, granulation, compaction, etc.),
• Function (product purpose and performance).
This approach enables cross-correlation (see Fig. 1.1) for a given crystalline
material’s or formulated drug product’s
• molecular and crystal structure,
• physical and chemical properties,
• processing behaviour,
• performance.

V. Ramachandran (*) • P.J. Halfpenny • K.J. Roberts

School of Chemical and Process Engineering, University of Leeds, Leeds LS2 9JT, UK
e-mail: v.ramachandran@leeds.ac.uk; p.j.halfpenny@btinternet.com; k.j.roberts@leeds.ac.uk

© Springer Science+Business Media B.V. 2017 3

K.J. Roberts et al. (eds.), Engineering Crystallography: From Molecule to Crystal
to Functional Form, NATO Science for Peace and Security Series A: Chemistry and
Biology, DOI 10.1007/978-94-024-1117-1_1
4 V. Ramachandran et al.

Fig. 1.1 The material

science tetrahedron, after
Sun [1] (Reproduced with Processing
the permission of Journal of
Pharmaceutical Science)

Structure

Properties

Performance

The above holistic approach forms the overall aim of this Erice Summer School
and in this brief introductory chapter the aim is to provide a short primer to the
attendees for those unfamiliar with basic concepts of crystal science. The materials
introduced here will underpin further chapters.

1.2 Crystals and Crystallography

1.2.1 Crystalline Solids

The principle differences between the three states of matter, solids, liquids and
gases, illustrated in Fig. 1.2, lie in the separation and mobility of the atoms or
molecules of which they are composed. In the gaseous state, molecules are highly
mobile and separated by large distances. In liquids, molecules are in close proxim-
ity but still retain substantial mobility. While in the solid-state, molecular motion is
typically limited to vibration and intermolecular distances are at a minimum
A crystal is a regular array of molecular entities, ordered in 3D where this degree
of order extends up to macroscopic dimensions. A single crystal is the one in which
this 3D order extends up to the sample’s physical size. In contrast, a polycrystalline
solid is the one where the crystal size is smaller than the actual sample size. In the
latter case the sample could be aggregate of a number of smaller micro-crystalline
grains such as an iron bar or a ceramic block, either of which could have a grain size
of ca. 1 μm. It should be noted that the atomic level properties of both poly- and
mono-crystalline solids are the same as the atomic-scale forces operate on the nm
scale size, at which level the difference in nature of the molecular interactions
between 1 μm3 (micro-crystal produced in industrial crystallisation reactors) or
1 Crystal Science Fundamentals 5

Fig. 1.2 Schematic diagram highlighting the differences between the gaseous (left), liquid
(centre) and solid (right) states of matter

100 cm3 (for electronic device materials) samples are negligible. Hence, the science
underlying the structure and crystallisation behaviour for both of these types of
materials, i.e. single crystals and polycrystalline solids is essentially the same.
Solids may be either crystalline or amorphous in nature. Crystalline solids are
characterised by long-range 3D order and exhibit a periodic three-dimensional
pattern in terms of the arrangement of the component atoms of the solid. The
structure of amorphous solids, in contrast, closely resembles that of the liquid
state. Although some short-range order may be present in amorphous solids, they
are best described as disordered. An amorphous solid is thermodynamically meta-
stable. It may transform to a crystalline structure if the kinetic barriers are not too
great. However, many amorphous materials, such as glass, have retained their
disordered structure for centuries. Materials with the same molecular structure
can also have different crystal structures and this is referred to as polymorphism.
For example, carbon forms crystals which can have one of three well known
structures: graphite, diamond and buckminsterfullerene.
The structural differences between the different polymorphic forms of crystals
and also those of amorphous forms of a given substance can give rise to substantial
differences in both their physical and chemical properties. The relationship between
structure and properties is a recurring theme which runs throughout this school.

1.2.2 Crystal Lattice

The simplest definition of a crystal is a 3D repeating pattern of atoms. The

schematic given in Fig. 1.3b represents a 2D pattern of a single butterfly being
repeated in the same orientation (a) which can be simply represented by an array of
circles.
The 2D pattern (butterfly) is called the motif and the points which make up the
array are called lattice points. One important feature of a lattice is that the
6 V. Ramachandran et al.

Fig. 1.3 A simple 2D pattern of a complex object (a butterfly) (a) together with its corresponding
lattice (b) as represented by circles

environment of each lattice point is identical. In order to describe the scheme of

repetition it is not, however, necessary to reproduce the entire lattice, but a small
representative part, such as the parallelogram shown more completely in 3D in
Fig. 1.4a. This still contains all the information necessary to define how the pattern
is repeated and can be fully described using only the lengths of the sides (a and b)
and the angle (γ) between the sides. This representative part of the lattice is referred
to as a unit cell, as shown in Fig 1.4b.
An entity or motif sitting at the lattice point could be an atom (e.g. for metallic or
elemental compounds), group of atoms (for complex atomic solid such as silicon
which has 2 atoms/lattice point), collection of ions (e.g. ionic solid such as K2SO4
would have 2 K+ and 1 SO42
ions at each lattice point) or a molecule (e.g. organic
compound would have complete molecule at each lattice point).
The key crystal science concepts are:
• Crystal ¼ Motif (what is being repeated) + Lattice (where to repeat),
• A more advanced definition of crystal ¼ Asymmetric unit (motif or what to
repeat) + Space group (how to repeat about the lattice points) + Wykoff positions
(where to repeat in the unit cell),
• Crystal lattice – infinite 3D array of points (lattice points),
• Unit cell – smallest reproducible unit within crystal lattice (Fig. 1.4),
• Lattice direction [uvw] – line drawn through lattice, where u, v, w are unit
vectors along three non- orthogonal directions (Fig. 1.5),
• Miller plane (hkl) – 2D surface cut through lattice (Fig. 1.6),
• Asymmetric unit – atom, molecule, ions, groups of molecules.
1 Crystal Science Fundamentals 7

(a) (b)
b c

β α
b b
γ
a γ

a a

Fig. 1.4 (a) The unit cell and lattice parameters of the two dimensional pattern and (b) a three-
dimensional unit cell, crystallographic axes a, b, c and the lattice parameters, a, b, c, α, β, γ

Fig. 1.5 Crystallographic

directions shown by
coloured arrows. A
direction is denoted by the
smallest coordinates of a
point through which the line
passes and usually the
smallest integer are used

Fig. 1.6 Crystallographic planes or Miller planes are denoted by the reciprocal of the fractional
coordinates of intercept of the plane with crystallographic axes
8 V. Ramachandran et al.

1.2.3 Crystal Systems

A vector ruvw in lattice with respect to the three (integer) vectors u, v, w is defined
as:
ruvw ¼ ua þ vb þ wc ð1:1Þ

a, b and c are lattice parameters defining the size and shape of the unit cell but are
not necessarily orthogonal. Hence, this is why we additionally need three angles to
define the unit cell. α – angle between b and c; β – angle between a and c, γ – angle
between a and b.
The inter-relationship between a, b, c, α, β and γ gives rise to a total of 7 crystal
systems as shown in Table 1.1. Examples of unit cells, Ibuprofen and D-mannitol,
are illustrated in Fig. 1.7.

Table 1.1 Seven crystal systems and examples

System Axial lengths and angles Example
Cubic a ¼ b ¼ c, α ¼ β ¼ γ ¼ 90 NaCl
Tetragonal a ¼ b 6¼ c, α ¼ β ¼ γ ¼ 90 TiO2, Urea
Orthorhombic a 6¼ b 6¼ c, α ¼ β ¼ γ ¼ 90 (NH4)2SO4
Rhombohedral or trigonal a ¼ b ¼ c, α ¼ β ¼ γ 6¼ 90 CaCO3, α-Quartz
Hexagonal a ¼ b 6¼ c, α ¼ β ¼ 90 , γ ¼ 120 Zn
Monoclinic a 6¼ b 6¼ c, α ¼ γ ¼ 90 6¼ β Paraffin, sucrose
Triclinic a 6¼ b 6¼ c, α 6¼ β 6¼ γ 6¼ 90 CuSO4 5(H2O)

Fig. 1.7 Examples of unit cells: (a) Ibuprofen [2] belonging to monoclinic structure with:
a ¼ 14.67, b ¼ 7.89, c ¼ 10.73, β ¼ 99.36; (b) D-mannitol [3] belonging to orthorhombic structure
with: a ¼ 8.67, b ¼ 16.88, c ¼ 5.56
1 Crystal Science Fundamentals 9

1.2.4 Crystal Chemistry

We now need to add the chemical nature of the material into our concept of the
crystal lattice. For a given molecule there are two dominant factors (Fig. 1.8) which
influence what crystal structure a given material might adopt:
These factors affect physical and crystallographic properties. We can subdivide
types of solid into five main groups of materials (see Fig. 1.9).

Fig. 1.8 Schematic

explaining crystal chemistry Crystal
with the key factors that Chemistry
affect the crystal structure

Size and Shape Nature of bonds

of molecules in between
crystal molecules

STRONG RELATIVE STRENGTH WEAK

HYDROGEN
COVALENT IONIC METALLIC MOLECULAR
BONDED
SOLIDS SOLIDS SOLIDS SOLIDS
SOLIDS

DIRECTED BONDS UNDIRECTED BONDS

Fig. 1.9 Schematic showing the major types of inter-molecular bonding expected in the solid-
state in relation to their relative strengths and their directional nature

Directed bonds tend to stop or restrict close packing which, in turn, makes for a
lower density solid when compared with similar materials which have undirected
bonds. The size of a molecule is reflected on the magnitude of the unit cell lattice
parameters; e.g. the molecular solid benzophenone [4] ((C6H5C ¼ O)2) has lattice
parameters of a ¼ 10.28, b ¼ 12.12, c ¼ 7.99 A (orthorhombic) whilst much smaller
atomic materials such as metal copper has a ¼ 3 Å (cubic). The shape of a molecule
reflects on the crystal system:
• Elemental compounds, such as metals and semiconductors, crystallising in high
symmetry crystal classes such as cubic and hexagonal.
• Irregularly shaped molecules, such as organic molecules and inorganic com-
plexes, crystallising in the lower symmetry triclinic, monoclinic classes.
The nature of bonding in any solid is of considerable importance since it
influences, either directly or indirectly, a wide range of properties, notably melting
10 V. Ramachandran et al.

point, crystal structure and mechanical properties. Most organic solids are molec-
ular in nature. While the atoms within a molecule are held together by strong
covalent bonds, the interatomic interactions are saturated and hence only weak
intermolecular forces exist between molecules. Many pharmaceutical compounds
are utilised in the form of salts and therefore exist as ionic species. In such cases, the
role of strong ionic interactions must also be considered.
Three factors are of particular importance in assessing the influence of
intermolecular bonding on the properties of organic solids:
• Strength of the interaction,
• Distance over which the interaction exerts an influence,
• Extent to which the bonding is directional.
Table 1.2 summarises the principle types of intermolecular bonding in organic
solids.

Table 1.2 Types of bonding in organic solids

Strength of Directed
Type Occurrence interactions Range interactions?
van der All atoms and molecules Weak short No
Waals (1–10 kJ/mol)
Dipole- Between polar molecules only Weak long No
dipole (3–4 kJ/mol)
Hydrogen Molecules containing O, N or F and a Strong short Yes
bonding hydrogen bonded to one of these elec- (10–40 kJ/mol)
tronegative atoms
Ionic Monatomic and molecular ions Strong short No
(10–50 kJ/mol)
Covalent Intramolecular interactions between Strong short Yes
atoms

In organic compounds bond strengths are characterised by:

• Strong intra-molecular bonds – robust molecules,
• Weak and isotropic inter-molecular bonds – soft solids with low melting point.
The bonding directionality is un-directed except for covalent crystals and where
there are H-bonds.
In summary, the main features that influence the organic solids are:
• Size of Molecules – large unit cells,
• Shape of Molecules – non-spherical shape,
• Nature of intermolecular forces – weak undirected,
• van der Waals bonds – close packed structures.
As a result, the organic crystalline solids have:
• Low melting point solids,
• Low symmetry crystallography,
• Polymorphic nature,
• Anisotropic deformation.
Another random document with
no related content on Scribd:
and although work has been begun, yet we [Sidenote: School
have but little expectation of its accomplishment at Robeson]
in a short time;
That there is a ... school at Maiden Creek kept by Thomas
Pearson, a Friend, who is at present engaged for a year, has
15 scholars entered for that time and 8 quarterly ditto scholars
at the rate of 40/ per annum for each, which is under the
direction of three overseers chosen by the employers. The
school house built on a piece of ground belonging to a Friend
which contains about five acres. There is likewise a school at
Reading kept by Benjamin Parks and wife in their own house;
they are members of the society and have about 50 scholars;
such as spell at 7/6 and others at 10/ per quarter but is not
under the direction of the meeting, nor are there any
overseers chosen to superintend the same, yet we are of the
mind a school established there under proper regulations and
care of the monthly meeting, might be useful and deserves
encouragement.
The schools within the verge of Robeson Monthly Meeting
are kept by a person who inclines to go to our meetings, has
about 20 scholars, amounting to about £34 per annum.
Endeavors are also used to get a school established there
upon a better plan and near the direction of the yearly
meeting, but how far they may be successful is at present
unknown. We do therefore recommend the whole to the
notion of alleviation of the Monthly Meeting as a matter
wherein friends are deeply interested.
Which we submit to the Meeting.
Amos Lee, Thomas Lightfoot, Samuel Hughes, Fannie
Ambree, Owen Hughes, (which was approved by the Monthly
Meeting, and decided that the substance be made a report to
the Quarterly Meeting—The Committee to be continued to the
service of Schools and report in the future).[339]
 Maiden Creek was at this time (1784) making [Sidenote: Maiden
earnest efforts to meet the standards set by the Creek secures
general meeting. In the eleventh month they land for school]
requested a number of persons to be named to [Sidenote:
whom they might give a deed of trust for the Attempt to
ground agreed upon for the use of their school.[340] establish school
at Reading]
Three were suggested and the deed and
declaration of trust accordingly drawn up. Efforts in the meantime
had been made towards establishing a school at Reading and a
committee to conduct a subscription for that purpose named.[341]
Help was solicited from the yearly meeting, but James Pemberton
answered for that body that there was no money to be spared at the
time, so Reading was advised to build such a house as their
circumstances would permit.[342] Near the close of 1787 those
having direct charge thereof made the following report of their
progress:
[Sidenote:
We the committee appointed to have the Committee report
school education of youth under care, have on Reading
given close attention to a school proposed to be school]
opened in a short time at Reading by Caleb Johnson, in a
house now in building by Friends there, and nearly finished,
which we are of the mind should be under particular care and
direction of the monthly meeting; and that it may be well that a
committee be thereby appointed to superintend and monthly
to visit said school; we have also drawn up and agreed on
certain rules to be observed and attended to by the
employers, master and scholars concerned therein for the
regulation and well ordering thereof: which we have ready for
the examination and inspection of the monthly meeting if
thought necessary. All which we submit thereto. Signed on
behalf of the committee, Francis Parvin.... Which minute
being read was allowed of and it was directed that a copy
thereof be kept in open view in said school and that the
original be lodged among the meeting papers; Benjamin
Pearson, Samuel Jackson, John Mears, Francis Parvin,
 Johannes Lee, Jr., and James Iddings are appointed to have
the said school under care and visit it once a month or oftener
as necessity may require and report of their care. The former
committee is continued.[343]

After the school had been in progress two years, [Sidenote: School
Samuel Jackson reported that it “appeared to be in discontinued]
an increasing way”[344] but its prosperity was not to
be long continued. In 1705 it was reported “discontinued,”[345] and
no reason assigned for it excepting “the situation of the Friends
there” which, taking into consideration the shortage of funds when it
was begun, we may infer, had reference to the financial situation.
The action of the monthly meeting in regard to it was left entirely to
their own judgment.[346]

SUMMARY
In this chapter we have considered the schools [Sidenote: Scope
of Philadelphia (city and county), and also those at of chapter]
Exeter Monthly Meeting, which belonged to the
Philadelphia Quarter.
Education in the Quaker colony was initially [Sidenote:
provided for in the instrument of government, Education to be
drawn up before the Proprietary left England; in function of
government]
accord with said provisions the first school
(Flower’s) was set up by the Council in 1683. [Sidenote: First
Thereafter, however, the initiative was usually school]
taken by the Quaker meeting, which in 1689 set up [Sidenote: School
a school and in 1697 applied for a charter under established by
the laws of the province. This petition was granted monthly meeting]
and Penn gave the first charter in 1701. Later
[Sidenote:
charters, in 1708 and 1711, granted extended Overseers made
privileges; by the last one the body of overseers independent]
were made self-perpetuating, and thus as
independent of the meeting as they wished to be. The letter said to
have been written to Thomas Lloyd, which credits Penn with
suggesting the school of 1689, has not yet been discovered.
The earliest masters were Keith, Makin, [Sidenote: Earliest
Pastorius, and Cadwalader. Mistresses were masters and
mentioned in connection with the schools from mistresses]
about 1699, Olive Songhurst being the first one [Sidenote: Growth
named. Salaries were not high and seem in some of system]
cases to have hardly sufficed for the family of the
master; increases were made upon complaint. Extra duties for the
teacher included keeping charge of the boys and girls in meeting.
From 1689 to 1779 the system increased from employing one to one
which required nine. In 1784 ten were reported.
Philadelphia Friends’ schools were first [Sidenote: Means
supported by (1) rates and (2) subscriptions, while of support]
(3) legacies and special gifts soon came to form a
considerable item in their support. Bequests were also a factor in the
support of the Negro School. Funds were occasionally raised by
bond issues, and derived from tenements built on school property.
Schools were first held in rented property and in [Sidenote: Place
the meeting house, but in 1698 steps were taken to of first schools]
purchase property of Lionell Brittain for the use of
schools. Property was received as a gift from [Sidenote:
Property by
Samuel Carpenter in 1701. The first record of a purchase and gift]
schoolhouse was the one to be begun in 1701. In
accord with their charter rights the power and [Sidenote:
Overseers more
independence of the overseers increased. In 1725 independent]
the monthly meeting conveyed to them all money
and the titles for all school property. The Negro School was provided
with a building in 1771. The end of the century is marked by the
establishment by the yearly meeting of a Boarding School at
Westtown in Chester County.
The exact date of Byberry’s first school is not [Sidenote:
determined; but must have been early, since Byberry]
Richard Brockden is reported to have been
schoolmaster there in 1711. School activity, however, seems to have
increased greatly near the middle of the century. The school was
under the care of a standing committee, which was to visit schools
every six weeks and make two reports thereon each year. Poor
children were schooled by the trustees of the school funds.
Germantown school began in 1702, though [Sidenote:
perhaps an evening school existed before that Germantown]
date. Pastorius continued in this school as master,
at least until 1718. The official language used in the school was
probably English. The names of the first patrons were all German; a
large number of English names among them in 1708 is an indication
of how the school and its master were regarded.
In 1758 youths’ meetings were established by [Sidenote: Exeter
Exeter, but no school committee was appointed Monthly]
until 1778. This committee accomplished nothing
[Sidenote:
and made no report of value. By a report of 1784, Maidencreek
Maidencreek, Reading, and Robeson were credited Reading
with one school each, which measured up in some Robeson]
ways to the desired standards. Exeter had none.
The Reading School was discontinued in 1795.
The total number of schools reported at Philadelphia,
Germantown, Byberry, and Exeter monthly meeting, was fifteen.
 CHAPTER V
SCHOOLS OF BUCKS COUNTY

The establishment of schools in Bucks County [Sidenote:

will be discussed (1) under the head of the monthly Schools of five
meetings therein situated and (2) in the order of monthly meetings
to be discussed]
their establishment in point of time. The several
monthly meetings and their dates of establishment, respectively, are
as follows: Falls, 1683; Middletown, 1683 (known as Neshaminy until
1706); Buckingham, set off from Falls, 1720; Wrightstown, set off
from Buckingham, 1734; and Richland, set off from Gwynedd (in
Montgomery County) in 1742.[347] Of these meetings, all were a part
of Bucks Quarterly Meeting save Richland, which belonged to that of
Abington.[348]
The first way in which the early Quakers usually [Sidenote:
looked after education was to arrange for a useful Apprenticeship
apprenticeship suitable to the individual, which was looked after by
meetings; placed
calculated to enable him or her to earn a living. The among Friends]
moral training was always considered when an
apprentice was to be placed. The placing of youths as apprentices
was in the charge of Friends appointed by the monthly meeting. The
early records of Falls Monthly Meeting show them active in regard to
this type of education. In 1704 this report was made before the
meeting.

A complaint having been made to this meeting that the

children of Abraham Clement are not placed out to the
satisfaction of Friends, it is the mind of this meeting that the
Friends formerly appointed do take care to speak with Samuel
Carpenter and Benjamin Collins about them, and make report
to next meeting.[349]
 A similar one of 1714 points out the continued interest and
attention in that respect.

It being proposed to this meeting that there is a necessity of

some Friends being appointed to take care about placing out
John Linton’s children as apprentices, therefore this meeting
doth appoint Joseph Kirkbride, Thomas Watson, Jr., and
Joseph Fell to care about placing them out.[350]

Another phase of education, more particularly [Sidenote: Moral

the moral, was cared for in the youths’ meetings, education in
which were established at intervals, usually not youths’ meetings;]
more than four or five times during the year. It was
the practice for the youths’ meetings to be established by the
quarterly meetings, in conjunction with representatives of the
monthly meetings. In 1713, Bucks Quarterly took up the re-
establishment of those within their limits, and ordered them
accordingly, as the following extract states.
[Sidenote:
It being thought necessary by this meeting established by
that the youths’ meeting be once a year at Bucks Quarterly]
Buckingham, once a year at Bristol and but
once a year at Falls and once at Middletown, therefore
agreed that they be on the days ... etc.[351]

To locate the date of the first school at Falls is [Sidenote:

difficult; it seems impossible to do so from the Question as to
information to be gleaned from the records. We early school at
Falls]
may be certain, however, that there was a school in
the neighborhood at a very early date, though we can hardly
determine the year. In 1730 the following request was made of the
meeting:

Some Friends of Falls Meeting requested to have the use

of the old schoolhouse, and it wanting repairing, they would
 repair it at their own charge, which is left to be considered at
next meeting.[352]

The presence in their vicinity, of an old [Sidenote:

schoolhouse which, moreover, needed repairs Contradiction in
before it could be used, would indicate that a the minutes of
Falls]
school had been there for a number of years.
Taking fifteen years as a very moderate span for the life of the
building, before it should need any considerable repairs we could
state with a good degree of assurance that the school building had
probably been built not later than 1715, and that the school dated
back to that time at the very latest.[353] But at the next meeting this
encounters a very dangerous obstruction. That meeting, referring to
the request of the seventh month, second, speaks of “the request
about having the old meetinghouse,” instead of, old schoolhouse.
[354] It further mentions that it was desired for the purpose of a

school.[355] From this it appears that the truth of our above

conclusion depends upon the accuracy of the records for seventh
month, second, 1730 and for eighth month, seventh, 1730. If the
record of the first date is correct our conclusion is unfounded and the
date for the first established school can probably be placed about
1730, or shortly thereafter.[356]
The records for the next thirty years reveal but [Sidenote: House
little of the activities of the schools in Falls Monthly for masters’
Meeting, though we are led to believe them in accommodation
proposed in 1759]
continuance, but perhaps not regularly. In 1759 the
meeting had agreed to allow a house to be built on [Sidenote:
their grounds for the accommodation of a school Property
conveyed to
master, but the house was not built there, since trustees for use of
Mahlon Kirkbride had already purchased some schools]
adjoining ground on which there was a house built
for that purpose.[357] The said Kirkbride offered to convey the same
property to some Friends, in trust for the meeting, and Robert Lucas,
Story Kirkbride, Mahlon Kirkbride, Jr., Jonathan Palmer, Jr., and
Edward Bayly, Jr., were appointed to receive the conveyance. This is
the first record of any permanent benefaction received. In 1783 the
urgent Advices of the Yearly Meeting being brought to their attention,
[358] a committee was appointed which reported the results of their
investigation up to that time in the following manner.
[Sidenote: Report
We, the committee appointed, in the first of school
month 1779 respecting the institution of schools committee]
for the instruction of our children in useful [Sidenote: Ground
learning, having conferred together ... agree to purchased for use
report that we have divers times met and had of school]
this important matter under our ... consideration,
and are desirous that this important subject and [Sidenote:
Standing
necessary care should meet with every proper committee on
encouragement and improvement; and we may education
recommended;
inform the meeting that there have been several and visitation]
improvements made on the lot of ground lately
purchased from Samuel Rhoads for the advantage of the
school and benefit of the master, and that the committee have
endeavored to encourage and pay for the schooling of such
poor children as are in the limits of the school kept at or near
this place whose parents are in low circumstances and are
willing to accept thereof. We have likewise extended our
consideration and views to the schools belonging to the other
preparative meetings, and although the circumstances of
things at present do not afford so promising and encouraging
a prospect as we could desire, yet we are desirous that every
proper encouragement may be afforded to promote the good
and necessary work, therefore, we are free to propose to the
meeting’s consideration that of having a standing committee
appointed for this purpose by the monthly meeting, and that
each preparative meeting should likewise appoint a
committee for the like purpose that should have this important
matter under their consideration in order to promote this so
necessary care in their respective meetings; and that the said
meeting’s committee should at proper and suitable times visit
the several preparative meetings’ schools and unite with the
said preparative meetings’ committees in affording and giving
 such help and assistance as to them from time to time may
appear necessary in order to promote this so good and
necessary a work and care. Signed at the desire and on
behalf of the committee, by James Moon.[359]

In accord with the above report the monthly [Sidenote:

meeting urged each preparative meeting to appoint Monthly meetings’
a committee on schools; the monthly meeting committee to join
those of the
named James Moon, John Merrick, Jonathan preparatives]
Kirkbride, William Satterthwaite, William Bidgood,
Jr., John Stapler and Joseph Gillingham to join with [Sidenote: Three
schools reported]
those of the preparatives for that service.[360] Five
months thereafter they reported,

The three several schools kept within compass of our

respective preparative meetings are conducted in some
measure under the care of a committee of Friends appointed
for that purpose and that the several teachers are members of
our society.[361]

The three preparative meetings were Falls, Makefield, and Bristol,

the last named being transferred to Middletown in 1788.[362]
Makefield Meeting was considerably assisted by help from private
sources; they reported to the monthly meeting in 1787:
[Sidenote:
We hereby inform the monthly meeting that Individual aid]
lately there has been a house built on the
ground belonging to Makefield Preparative Meeting for the
accommodation of a school master, chiefly at the expense of
Bernard Taylor, which he is desirous should be under use for
that purpose, to be subject to a moderate yearly rent to be
paid to Friends of that meeting for the use of the said
meeting: the said house to be their property and under the
care and the direction of said meeting with the advice and
 assistance of the Falls Monthly Meeting as occasion may
require.[363]

In 1790 a committee of the quarterly meeting [Sidenote: New

was appointed to confer with those of the monthly building proposed
meetings on schools, hoping that the union of all at Falls; not built
till later]
might be more productive of results than all
working separately.[364] In 1794 plans were set on foot for a new
schoolhouse at Falls Preparative, said house to be two stories in
height and about twenty-two feet by thirty.[365] It was to be placed
“near the line” of the meeting’s land at the west end of the meeting
house. The monthly meeting was to pay £75, the employers who are
members, £75, and the school committee £50 from the money
arising from donations left for the purposes of schools. The house
was not built until 1799, due to some unknown delay; its dimensions
were twenty-four by twenty-six feet, one story high, with a cellar of
the same dimensions.[366]
In 1797 the attention of the monthly meeting was [Sidenote:
called to the proposals of the yearly meeting for the Attention called to
the boarding
founding of a boarding school.[367] Copies of the school]
printed rules proposed for its government had been
received, and a committee was appointed to distribute them and to
take subscriptions from any who were interested to contribute.[368]
The problem of school support occupied a [Sidenote:
considerable part of Falls Meeting’s time. The Support of
means of support were here, as in others already schools
Monthly]
in Falls
mentioned, (1) subscriptions, (2) donations and (3)
rates. In 1760 it was considered necessary to appoint a committee of
fourteen members to take an inventory of all legacies and donations,
lands and benefactions which had been left to the meeting.[369]
Some had been given for definitely stated uses; and others allowed
the application to be determined by the members of the meeting. It
was the will of the assembly that the committee appointed should
especially determine what funds might be applied to the use of the
schools. They reported at the next meeting that the legacy left by
Elinor Bryner might be applied to the use of schools, along with
those given definitely for that purpose.[370] The method by which the
funds were to be applied to that use were indicated in the
suggestions of the committee at a later meeting, as follows:
[Sidenote: A
We ... are of the opinion that the most that committee to
can be done at present, will be to appoint have oversight of
Friends to have the care of the schools and to education
poor]
of the

examine what poor children may be amongst

us, they being the proper objects of the charity designated by
the givers of the money, and that the said Friends have power
to agree with a master to teach such children; and also to
draw orders for the payment thereof out of the interest arising
from the money appropriated to the use of schools.
Nominated seven Friends for that service and submitted the
names and the report to the monthly meeting. The Friends
above named are appointed to that service with the powers
therein mentioned and are desired to lay an account before
the monthly meeting at least once in each year and oftener if
the meeting shall see fit to call for it.[371]

Such a plan as here indicated was consistently followed

throughout the century in regard to school support. The interest on
legacies had to be paid annually.[372]
In 1781 the meeting was advised that Samuel [Sidenote:
Rhoads of Philadelphia had offered to sell four Rhoads proposes
acres of ground adjoining the schoolhouse lot, to to sell land for a
school;
be used for the promotion of the school, and the considered]
benefit of the schoolmasters.[373] The
consideration asked was £60, and Rhoads and his two brothers-in-
law, Joseph Pemberton and Samuel Pleasants, offered to donate
£20, making it cost the meeting but £40. The committee on school
support was directed to consider this proposal. Bristol Preparative
also received very valuable assistance for the use of poor children’s
schooling, in the bequest of £50 Pennsylvania currency which was
left them by John Baldwin of Philadelphia.[374] The great concern of
the meeting for the best expenditure of these donations for educating
not only the poor Whites but also the Negroes, is seen in their
minute of 1787.[375] Careful account was kept and the accounts
frequently audited, sometimes at the request of individuals.[376] In
1790 the committee reported their concerns as follows:
[Sidenote: Report
We the committee appointed by the monthly of committee on
meeting to have the care of schooling poor education of the
children; also to have the distribution of the poor]
interests accruing on the several donations given for that use,
have given attention to the service to which we were
appointed: and the schooling a considerable number of
children has accordingly been paid for, but as it is allowed that
a change of the teacher at times may be useful or
advantageous to a school, we are united in the sentiment that
if such a change was to take place in the school kept at this
place, it would be a means whereby the school might be
considerably enlarged and the design and end of the several
donations left for the use of the said school more fully
answered. (Report submitted and accepted and the
committee continued to the further service.)[377]

The establishment of these permanent funds [Sidenote:

was frequently expressed by the numerous Establishment of
committees as the most important consideration for funds of basic
importance]
the execution of the school idea. They attempted
again and again to provide a uniform means of establishing such
funds, but due to the unequal circumstances of the several meetings
it was impossible to do so.[378] The uniform plan was kept as an
ideal to be striven for and recommended to the quarterly meeting for
its advisement in the matter;[379] in the meantime individual
contributions were urged on all who felt inclined to endow a worthy
cause.[380] The amounts given were frequent though small, many of
them being about £5.[381]
 In addition to the local expenses of the meetings, (1) for worship,
(2) for the use of schools, (3) for the maintenance of the poor, etc.,
there were also quotas to be raised for the yearly meeting stock,
which added materially to the burden of each of the preparative
meetings. The quota for the meetings belonging to Falls in 1797 was
£500.[382]
If we may look over the Quaker treasurer’s shoulder as he runs his
accounts at the end of the century, we find him situated financially as
follows:
[Sidenote:
We the committee appointed to examine and Financial status of
settle the Treasurer’s accounts, having Falls at end of
attended thereto, find a balance in his hands of century]
£136/8/11 school money; also, £3/10/7 poor money; and
£9/00/00 of interest received on John Large’s legacy, making
the whole £148/19/6, in the treasurer’s hands, and the monies
upon interest stand as in the following statement, viz.

Bonds for School Money

1 bond for ” ” £250/
1 ” ” ” £7/9/4½
1 legacy without a bond £50
1 bond for ” ” £50
1 ” ” ” £50
1 ” ” ” £130
1 ” ” ” £100
1 ” ” ” £50
1 ” ” ” £40
Included in a bond of £75 £40
£777/9/4½

Interest due on school money £40/00/11

And one year’s rent on house and lot £12/00/00
And one year’s rent on house and lot £12/00/00[383]
 The Middletown Meeting began its educational [Sidenote:
work more promptly than did Falls.[384] Ten years Middletown]
after the first establishment of the meeting a
request was brought forward as follows:
[Sidenote: School
Some Friends have signified the likeliness of requested in
having a schoolmaster hereabouts to instruct Middletown
children and also requested that they might meeting house]
have the privilege to teach in the meeting house, to which this
meeting does give their free consent, provided it be no
hindrance to Friends Meetings.[385]

It is quite probable that the school established as [Sidenote: Again

requested, was a temporary and irregular affair, requested]
depending on the will of the individual patrons.
Certainly, it had not any official connection with the meeting, and
probably did not have for many years. In 1699, a request similar to
that of 1693 was made by Thomas Stackhouse and others, desiring
the use of the meeting house for a schoolmaster,[386] which implies
they had not advanced much beyond their state of 1693. This
request was likewise granted, provided no hindrance be caused to
the meetings.
Because of very inadequate records in this [Sidenote:
regard, much is left to be surmised concerning the Middletown not in
continuation of the schools thus early begun. The harmony with
yearly meeting’s
meeting was in continual touch with the desires proposals]
and proposals of the yearly meeting,[387] and it
does not seem justifiable to suppose that education languished,
because scant records of it remain. The general tone of their minutes
is one of self-satisfaction, and implies that they themselves were well
pleased with their state. The elaborate recommendations of the
yearly meeting in 1750[388] did not meet with their approval as they
thought it quite impossible for those members living remote in the
country districts.[389] That they disagreed with the plan indicates
neither a lack of interest in the subject, nor a lack of schools in their
locality. Rather, it may indicate the opposite.
In 1755 there was made the first donation to a [Sidenote:
permanent foundation for a free school. At a Donation 1755 for
meeting in that year an extract of Adam Harker’s a free school]
will was produced, where it appeared he had, [Sidenote: Under
control of monthly
meeting]
given a sum of money to them with others in
trust to be employed toward raising a fund for settling and
maintaining a Free School under the care and direction of this
meeting ... shall and will therewith purchase an annuity or
yearly ground rent, or in such other manner as they may think
most proper employ the said sum (£40) towards raising a fund
for settling and maintaining a Free School in Middletown
aforesaid, under the direction and control of the monthly
Meeting of Friends there.[390]

Whether there was a new school erected as a result of the

bequest or whether it was turned to the use of one already existing
does not appear; the latter suggestion is much the more probable.
The advices of 1777 and 1778 and the years following aroused the
members to the responsibilities which they must accept. In 1779 they
made report as follows:

Although it appears that the education of the youth has

been too much neglected, we believe there is an increasing
care that Friends may be more careful in that weighty
concern.[391]

And in 1780:

We believe a good degree of care is taken by some in

regard to the education of those under their care, and that an
increase in that is necessary.[392]
 All questions in regard to schools or educational [Sidenote: All
affairs whatsoever were dismissed summarily, and details under the
given to the charge of the committee on schools. care of a
[393] A committee reported in 1782 that nothing had committee on
schools]
been done more than to visit the school they
already had.[394] The failure to bring forth results may have been
with the committee; at any rate the meeting decided to try a new
one.
[Sidenote: New
This meeting taking into consideration the committee
several matters recommended in the extracts ... appointed]
respecting the education of the youth and their
school tuition, are of the opinion that a reappointment on
those important subjects is necessary; wherefore, Woolston J.
Paxson, W. Blakeley, J. Watson and R. Hartshorne are
appointed as committee to those services, and they are
desired to closely attend thereto in order that the present and
former advices may be carried as fully into execution as
possible.[395]

In 1785 this committee reported that visits had [Sidenote:

been made to families in the interests of education Activities of the
committee not
but that little was effected.[396] The committee was effective]
released and the consideration of education left to
the next meeting,[397] at which a new committee of three was
appointed. This one, so far as their record goes, was neither more
active nor more successful than the others. In 1788 they report
“nothing much has been done in respect to schools since last year,”
which report was sent to the yearly meeting.[398] The record is not
complete to the end of the century, but for the period considered
does not offer any evidence of more than passing educational
interest and activity. Nothing unusual is to be noted in the finance
and support of the school at Middletown. Mention was made of
Harker’s will, which, it seems, was the first legacy left to its benefit.
[399]
 The attention of the meeting was early given to [Sidenote: Care of
the care of the orphans and the poor, and poor orphan;
especially to their satisfactory placement among apprenticing]

people as apprentices. The following from the

records for 1699 will serve for illustration.

It is agreed and concluded upon by this meeting that the

meeting take care of all Friends children that are left as
orphans and unsettled, to inspect and see that all such be
taken care of and settled in the best and suitablest manner
according to their capacity, that thereby they may discharge
their duty and all such be eased by taking such due care....

The attention of Buckingham Meeting was also [Sidenote:

turned toward the education of apprentices, and Buckingham]
careful scrutiny given those who removed to
[Sidenote:
apprentice themselves elsewhere, as also those Apprentices; care
who removed to Buckingham Meeting. In 1764 in their
Mahlon Michener, son of John, removed his certification]
certificate to Philadelphia, “having been placed as
apprentice” in the vicinity of that meeting.[400] John Parry, minor, an
apprentice to Thomas Fell, blacksmith, produced a certificate in
Abington Monthly,[401] which was accepted and also that of Isaac
Gommere from the same place.[402] The poor were provided for by
the legacy left for that purpose by John Holcomb in 1749.[403]
Whether this might, a part of it, have been spent for schooling is not
known.
In 1755 there was a minute entered in the [Sidenote: Harker
records to the effect that a legacy had been left to legacy for a free
Buckingham by their deceased friend Adam school]
Harker, for the purpose of establishing a free [Sidenote:
school in that place.[404] The amount of the Committee
bequest was the same (£40) as that left to the appointed
schools]
on

Middletown Meeting by Harker.[405] This was the

first bequest for definite school purposes; the indications are that
many followed. In 1778, a minute gives their financial status as
£244/4/11½ and they entertained a proposition and concluded to
raise £500 more.[406] At the same time, the recommendations from
the yearly meeting being read,[407] a committee of the following
persons was appointed for investigation and assistance on the
subject of schools, viz.: Paul Preston, Joseph Watson, Joseph
Preston, John Gillingham, Benjamin Paxson, Benjamin Kinsey,
Thomas Watson, Joseph Eastburn, John Kinsey, John Balderston,
Jonathan Shaw, Benjamin Cutler, Thomas Good, Jr., John Brown,
and Robert Kirkbride.[408] The action of this committee is not brought
out in the minutes of the meeting.
The quarterly meeting made a new appeal in [Sidenote: Visiting
1780 for a more decided action by the various schools required]
tributary meetings which was followed by the
appointment of a new committee.[409] They were requested to “visit
the school” for the “help and assistance” of the master and to report
their action to a future meeting. In the twelfth month of the same year
they made these recommendations:
[Sidenote:
The committee appointed for the proper Committee’s
establishment and regulation of schools made recommendations
report in writing that it is their sense and ]
judgment that the monthly meeting should recommend to the
particular meetings severally, to promote subscriptions toward
the setting up and building upon their meeting’s lands as may
be convenient for schoolhouses and such conveniences as
may accommodate settled persons who live near the same,
as also to encourage their contributions toward making up
funds or salaries for the constant support of schools therein
which is recommended to the preparative meetings.[410]

A new committee was appointed in 1784.[411] [Sidenote:

They convened with the committees of the Appointment of
trustees
preparatives and discussed the recommendations necessary]
and means suggested by the yearly meeting. Their
conclusion was to the effect that one thing in the recommendations
was absolutely necessary, namely, that all funds, legacies,
properties, etc., provided for the schools, should be vested in
trustees for that purpose.[412] Without taking this step they saw no
way to attain even the least success. It was further suggested that
the trustees or committee thus appointed should investigate the
present houses for schools, their condition and location, in each of
the particular meetings, that a wiser plan might be followed in
locating the new ones. The meeting considering the report decided
to adopt its suggestions and accordingly appointed thirteen men,

to inspect into the state of such schools as are now kept and
where it may be necessary, to promote others,

and make a report as soon as possible.[413] Its report, produced in

the first month, 1785, was quite long. Only the essential points of it
are given in the following digest.[414]
1. Most of the committee appointed met and [Sidenote:
decided to confirm the former committee’s report. Summary of
committee’s
2. We find that there are many schoolhouses report of 1785]
within the bounds that include the members of the
meeting.

a. These are not well situated for the service of schools.

b. Some are well situated, however, as (1) one on land
granted by Samuel Eastburn and vested in the school
trustees, (2) one on land granted by Thomas Goode, vested
in members of the meeting, but not in trust for the meeting.

3. They suggest that these two houses be used as previously and

that new houses be erected not more than three miles apart.
4. They maintain an uncertain state has prevailed among the
schools.