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Mass Spectrometry
Third Edition
Mass Spectrometry
Principles and Applications
Third Edition
Edmond de Hoffmann
Université Catholique de Louvain, Belgium & Ludwig Institute for
Cancer Research, Brussels, Belgium
Vincent Stroobant
Ludwig Institute for Cancer Research, Brussels, Belgium
Copyright
C 2007 John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester,
West Sussex PO19 8SQ, England
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Library of Congress Cataloging-in-Publication Data

Hoffmann, Edmond de.
[Spectrométrie de masse. English]
Mass spectrometry : principles and applications. – 3rd ed. / Edmond de Hoffmann, Vincent Stroobant.
p. cm.
Includes bibliographical references and index.
ISBN 978-0-470-03310-4
1. Mass spectrometry. I. Stroobant, Vincent. II. Title.
QD96.M3 H6413 2007

573 .65 — dc22
2007021691
British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library
ISBN 978-0-470-03310-4 (HB)
ISBN 978-0-470-03311-1 (PB)
Typeset in 10/12pt Times by Aptara Inc., New Delhi, India
Printed and bound in Great Britain by Antony Rowe Ltd, Chippenham, Wiltshire
This book is printed on acid-free paper responsibly manufactured from sustainable forestry
in which at least two trees are planted for each one used for paper production.
Contents
Preface xi
Introduction 1
Principles 1
Diagram of a Mass Spectrometer 4
History 5
Ion Free Path 10
1 Ion Sources 15
1.1 Electron Ionization 15
1.2 Chemical Ionization 17
1.2.1 Proton transfer 19
1.2.2 Adduct formation 21
1.2.3 Charge-transfer chemical ionization 21
1.2.4 Reagent gas 22
1.2.5 Negative ion formation 25
1.2.6 Desorption chemical ionization 27
1.3 Field Ionization 28
1.4 Fast Atom Bombardment and Liquid Secondary Ion Mass Spectrometry 29
1.5 Field Desorption 31
1.6 Plasma Desorption 32
1.7 Laser Desorption 33
1.8 Matrix-Assisted Laser Desorption Ionization 33
1.8.1 Principle of MALDI 33
1.8.2 Practical considerations 36
1.8.3 Fragmentations 39
1.8.4 Atmospheric pressure matrix-assisted laser desorption ionization 39
1.9 Thermospray 41
1.10 Atmospheric Pressure Ionization 42
1.11 Electrospray 43
1.11.1 Multiply charged ions 46
1.11.2 Electrochemistry and electric field as origins of multiply charged ions 48
1.11.3 Sensitivity to concentration 50
1.11.4 Limitation of ion current from the source by the electrochemical process 51
1.12 Atmospheric Pressure Chemical Ionization 55
1.13 Atmospheric Pressure Photoionization 56
v
vi CONTENTS
1.14 Atmospheric Pressure Secondary Ion Mass Spectrometry 61

1.14.1 Desorption electrospray ionization 61
1.14.2 Direct analysis in real time 62
1.15 Inorganic Ionization Sources 65
1.15.1 Thermal ionization source 65
1.15.2 Spark source 67
1.15.3 Glow discharge source 68
1.15.4 Inductively coupled plasma source 69
1.16 Gas-Phase Ion-Molecule Reactions 72
1.17 Formation and Fragmentation of Ions: Basic Rules 76
1.17.1 Electron ionization and photoionization under vacuum 77
1.17.2 Ionization at low pressure or at atmospheric pressure 77
1.17.3 Proton transfer 77
1.17.4 Adduct formation 78
1.17.5 Formation of aggregates or clusters 79
1.17.6 Reactions at the interface between source and analyser 79
2 Mass Analysers 85
2.1 Quadrupole Analysers 88
2.1.1 Description 88
2.1.2 Equations of motion 91
2.1.3 Ion guide and collision cell 96
2.1.4 Spectrometers with several quadrupoles in tandem 98
2.2 Ion Trap Analysers 100
2.2.1 The 3D ion trap 100
2.2.2 The 2D ion trap 117
2.3 The Electrostatic Trap or ‘Orbitrap’ 122
2.4 Time-of-Flight Analysers 126
2.4.1 Linear time-of-flight mass spectrometer 126
2.4.2 Delayed pulsed extraction 129
2.4.3 Reflectrons 131
2.4.4 Tandem mass spectrometry with time-of-flight analyser 134
2.4.5 Orthogonal acceleration time-of-flight instruments 139
2.5 Magnetic and Electromagnetic Analysers 143
2.5.1 Action of the magnetic field 143
2.5.2 Electrostatic field 144
2.5.3 Dispersion and resolution 145
2.5.5 Tandem mass spectrometry in electromagnetic analysers 149
2.6 Ion Cyclotron Resonance and Fourier Transform Mass Spectrometry 157
2.6.1 General principle 157
2.6.2 Ion cyclotron resonance 159
2.6.3 Fourier transform mass spectrometry 159
2.6.4 MSn in ICR/FTMS instruments 164
2.7 Hybrid Instruments 164
2.7.1 Electromagnetic analysers coupled to quadrupoles or ion trap 165
2.7.2 Ion trap analyser combined with time-of-flight or ion cyclotron
resonance 166
2.7.3 Hybrids including time-of-flight with orthogonal acceleration 167
CONTENTS vii
3 Detectors and Computers 175

3.1 Detectors 175
3.1.1 Photographic plate 176
3.1.2 Faraday cup 176
3.1.3 Electron multipliers 177
3.1.4 Electro-optical ion detectors 181
3.2 Computers 182
3.2.1 Functions 183
3.2.2 Instrumentation 183
3.2.3 Data acquisition 183
3.2.4 Data conversion 186
3.2.5 Data reduction 186
3.2.6 Library search 186
4 Tandem Mass Spectrometry 189

4.1 Tandem Mass Spectrometry in Space or in Time 189
4.2 Tandem Mass Spectrometry Scan Modes 192
4.3 Collision-Activated Decomposition or Collision-Induced Dissociation 195
4.3.1 Collision energy conversion to internal energy 196
4.3.2 High-energy collision (keV) 198
4.3.3 Low-energy collision (between 1 and 100 eV) 199
4.4 Other Methods of Ion Activation 199
4.5 Reactions Studied in MS/MS 202
4.6 Tandem Mass Spectrometry Applications 204
4.6.1 Structure elucidation 205
4.6.2 Selective detection of target compound class 207
4.6.3 Ion–molecule reaction 210
4.6.4 The kinetic method 211
5 Mass Spectrometry/Chromatography Coupling 217

5.1 Elution Chromatography Coupling Techniques 218
5.1.1 Gas chromatography/mass spectrometry 219
5.1.2 Liquid chromatography/mass spectrometry 221
5.1.3 Capillary electrophoresis/mass spectrometry 228
5.2 Chromatography Data Acquisition Modes 228
5.3 Data Recording and Treatment 230
5.3.1 Data recording 230
5.3.2 Instrument control and treatment of results 232
6 Analytical Information 243

6.1 Mass Spectrometry Spectral Collections 243
6.2 High Resolution 245
6.2.1 Information at different resolving powers 249
6.2.2 Determination of the elemental composition 251
6.3 Isotopic Abundances 251
6.4 Low-mass Fragments and Lost Neutrals 257
6.5 Number of Rings or Unsaturations 258
6.6 Mass and Electron Parities, Closed-shell Ions and Open-shell Ions 259
6.6.1 Electron parity 259
6.6.2 Mass parity 259
6.6.3 Relationship between mass and electron parity 260
viii CONTENTS
6.7 Quantitative Data 260

6.7.1 Specificity 260
6.7.2 Sensitivity and detection limit 262
6.7.3 External standard method 264
6.7.4 Sources of error 265
6.7.5 Internal standard method 266
6.7.6 Isotopic dilution method 268
7 Fragmentation Reactions 273

7.1 Electron Ionization and Fragmentation Rates 273
7.2 Quasi-Equilibrium and RRKM Theory 275
7.3 Ionization and Appearance Energies 279
7.4 Fragmentation Reactions of Positive Ions 280
7.4.1 Fragmentation of odd-electron cations or radical cations (OE•+ ) 280
7.4.2 Fragmentation of cations with an even number of electrons (EE+ ) 286
7.4.3 Fragmentations obeying the parity rule 288
7.4.4 Fragmentations not obeying the parity rule 291
7.5 Fragmentation Reactions of Negative Ions 291
7.5.1 Fragmentation mechanisms of even electron anions (EE– ) 292
7.5.2 Fragmentation mechanisms of radical anions (OE•− ) 293
7.6 Charge Remote Fragmentation 293
7.7 Spectrum Interpretation 294
7.7.1 Typical ions 296
7.7.2 Presence of the molecular ion 296
7.7.3 Typical neutrals 296
7.7.4 A few examples of the interpretation of mass spectra 298
8 Analysis of Biomolecules 305

8.1 Biomolecules and Mass Spectrometry 305
8.2 Proteins and Peptides 306
8.2.1 ESI and MALDI 307
8.2.2 Structure and sequence determination using fragmentation 309
8.2.3 Applications 324
8.3 Oligonucleotides 342
8.3.1 Mass spectra of oligonucleotides 343
8.3.2 Applications of mass spectrometry to oligonucleotides 346
8.3.3 Fragmentation of oligonucleotides 351
8.3.4 Characterization of modified oligonucleotides 355
8.4 Oligosaccharides 357
8.4.1 Mass spectra of oligosaccharides 358
8.4.2 Fragmentation of oligosaccharides 360
8.4.3 Degradation of oligosaccharides coupled with mass spectrometry 367
8.5 Lipids 371
8.5.1 Fatty acids 373
8.5.2 Acylglycerols 376
8.5.3 Bile acids 382
8.6 Metabolomics 386
8.6.1 Mass spectrometry in metabolomics 387
8.6.2 Applications 388
CONTENTS ix
9 Exercises 403
Questions 403
Answers 415
Appendices 437
1 Nomenclature 437
1.1 Units 437
1.2 Definitions 437
1.3 Analysers 438
1.4 Detection 439
1.5 Ionization 440
1.6 Ion types 441
1.7 Ion–molecule reaction 442
1.8 Fragmentation 442
2 Acronyms and abbreviations 442
3 Fundamental Physical Constants 446
4A Table of Isotopes in Ascending Mass Order 447
4B Table of Isotopes in Alphabetical Order 452
5 Isotopic Abundances (in %) for Various Elemental Compositions CHON 457
6 Gas-Phase Ion Thermochemical Data of Molecules 467
7 Gas-Phase Ion Thermochemical Data of Radicals 469
8 Literature on Mass Spectrometry 470
9 Mass Spectrometry on Internet 476
Index 479
Preface to Third Edition
Following the first studies of J.J. Thomson (1912), mass spectrometry has undergone count-
less improvements. Since 1958, gas chromatography coupled with mass spectrometry has
revolutionized the analysis of volatile compounds. Another revolution occurred in the 1980s
when the technique became available for the study of non-volatile compounds such as pep-
tides, oligosaccharides, phospholipids, bile salts, etc. From the discoveries of electrospray
and matrix-assisted laser desorption in the late 1980s, compounds with molecular masses
exceeding several hundred thousands of daltons, such as synthetic polymers, proteins, gly-
cans and polynucleotides, have been analysed by mass spectrometry.
From the time of the second edition published in 2001 until now, much progress has
been achieved. Several techniques have been improved, others have almost disappeared.
New atmospheric pressure desorption ionization sources have been discovered and made
available commercially. One completely new instrument, the orbitrap, based on a new mass
analyser, has been developed and is now also available commercially. Improved accuracy
in low-mass determination, even at low resolution, improvements in sensitivity, better de-
tection limits and more efficient tandem mass spectrometry even on high-molecular-mass
compounds are some of the main achievements. We have done our best to include them is
this new edition.
As the techniques continue to advance, the use of mass spectrometry continues to grow.
Many new applications have been developed. The most impressive ones arise in system
biology analysis.
Starting from the very foundations of mass spectrometry, this book presents all the
important techniques developed up to today. It describes many analytical methods based
on these techniques and emphasizes their usefulness by numerous examples. The reader
will also find the necessary information for the interpretation of data. A series of graduated
exercises allows the reader to check his or her understanding of the subject. Numerous
references are given for those who wish to go deeper into some subjects. Important Internet
addresses are also provided. We hope that this new edition will prove useful to students,
teachers and researchers.
We would like to thank Professor Jean-Louis Habib Jiwan and Alexander Spote for their
friendly hospitality and competent help.
We would also like to acknowledge the financial support of the FNRS (Fonds National
de la Recherche Scientifique, Brussels).
Many colleagues and friends have read the manuscript and their comments have been
very helpful. Some of them carried out a thorough reading. They deserve special mention:
xi
xii PREFACE TO THIRD EDITION
namely, Magda Claeys, Bruno Domon, Jean-Claude Tabet, and the late François Van Hoof.
We also wish to acknowledge the remarkable work done by the scientific editors at John
Wiley & Sons.
Many useful comments have been published on the first two editions, or sent to the editor
or the authors. Those from Steen Ingemann were particularly detailed and constructive.
Finally, we would like to thank the Université Catholique de Louvain, the Ludwig
Institute for Cancer Research and all our colleagues and friends whose help was invaluable
to us.
Edmond de Hoffmann and Vincent Stroobant

Louvain-la-Neuve, March 2007
Introduction
Mass spectrometry’s characteristics have raised it to an outstanding position among analyti-

cal methods: unequalled sensitivity, detection limits, speed and diversity of its applications.
In analytical chemistry, the most recent applications are mostly oriented towards bio-
chemical problems, such as proteome, metabolome, high throughput in drug discovery
and metabolism, and so on. Other analytical applications are routinely applied in pollu-
tion control, food control, forensic science, natural products or process monitoring. Other
applications include atomic physics, reaction physics, reaction kinetics, geochronology,
inorganic chemical analysis, ion–molecule reactions, determination of thermodynamic pa-
rameters (G◦ f , K a , etc.), and many others.
Mass spectrometry has progressed extremely rapidly during the last decade, between
1995 and 2005. This progress has led to the advent of entirely new instruments. New
atmospheric pressure sources were developed [1–4], existing analysers were perfected and
new hybrid instruments were realized by new combinations of analysers. An analyser based
on a new concept was described: namely, the orbitrap [5] presented in Chapter 2. This has
led to the development of new applications. To give some examples, the first spectra of
an intact virus [6] and of very large non-covalent complexes were obtained. New high-
throughput mass spectrometry was developed to meet the needs of the proteomic [7, 8],
metabolomic [9] and other ‘omics’.
Principles
The first step in the mass spectrometric analysis of compounds is the production of gas-
phase ions of the compound, for example by electron ionization:
M + e− −→ M•+ + 2e−
This molecular ion normally undergoes fragmentations. Because it is a radical cation

with an odd number of electrons, it can fragment to give either a radical and an ion with an
even number of electrons, or a molecule and a new radical cation. We stress the important
difference between these two types of ions and the need to write them correctly:
EE+ + R⋅
EVEN ION RADICAL
M⋅+
OE⋅+ + N
ODD ION MOLECULE
These two types of ions have different chemical properties. Each primary product ion
derived from the molecular ion can, in turn, undergo fragmentation, and so on. All these
ions are separated in the mass spectrometer according to their mass-to-charge ratio, and
Mass Spectrometry: Principles and Applications, Third Edition Edmond de Hoffmann and Vincent Stroobant

C Copyright 2007, John Wiley & Sons Ltd
2 INTRODUCTION
m/z Relative m/z Relative

abundance (%) abundance (%)
12 0.33 28 6.3
13 0.72 29 64
14 2.4 30 3.8
15 13 31 100
16 0.21 32 66
17 1.0 33 0.73
18 0.9 34 ~ 0.1
Figure 1
Mass spectrum of methanol by electron ion-
ization, presented as a graph and as a table.
are detected in proportion to their abundance. A mass spectrum of the molecule is thus
produced. It provides this result as a plot of ion abundance versus mass-to-charge ratio.
As illustrated in Figure 1, mass spectra can be presented as a bar graph or as a table. In
either presentation, the most intense peak is called the base peak and is arbitrarily assigned
the relative abundance of 100 %. The abundances of all the other peaks are given their
proportionate values, as percentages of the base peak. Many existing publications label the
y axis of the mass spectrum as number of ions, ion counts or relative intensity. But the term
relative abundance is better used to refer to the number of ions in the mass spectra.
Most of the positive ions have a charge corresponding to the loss of only one electron. For
large molecules, multiply charged ions also can be obtained. Ions are separated and detected
according to the mass-to-charge ratio. The total charge of the ions will be represented by
q, the electron charge by e and the number of charges of the ions by z:
q = ze and e = 1.6 × 10−19 C
The x axis of the mass spectrum that represents the mass-to-charge ratio is commonly
labelled m/z. When m is given as the relative mass and z as the charge number, both of
which are unitless, m/z is used to denote a dimensionless quantity.
Generally in mass spectrometry, the charge is indicated in multiples of the elementary
charge or charge of one electron in absolute value (1 e = 1.602 177 × 10−19 C) and the mass
is indicated in atomic mass units (1 u = 1.660 540 × 10−27 kg). As already mentioned, the
physical property that is measured in mass spectrometry is the mass-to-charge ratio. When
the mass is expressed in atomic mass units (u) and the charge in elementary charge units
PRINCIPLES 3
(e) then the mass-to-charge ratio has u/e as dimensions. For simplicity, a new unit, the
Thomson, with symbol Th, has been proposed [10]. The fundamental definition for this
unit is
1 Th = 1 u/e = 1.036 426 × 10−8 kg C−1
Ions provide information concerning the nature and the structure of their precursor
molecule. In the spectrum of a pure compound, the molecular ion, if present, appears at the
highest value of m/z (followed by ions containing heavier isotopes) and gives the molecular
mass of the compound. The term molecular ion refers in chemistry to an ion corresponding
to a complete molecule regarding occupied valences. This molecular ion appears at m/z 32
in the spectrum of methanol, where the peak at m/z 33 is due to the presence of the 13 C
isotope, with an intensity that is 1.1 % of that of the m/z 32 peak. In the same spectrum, the
peak at m/z 15 indicates the presence of a methyl group. The difference between 32 and
15, that is 17, is characteristic of the loss of a neutral mass of 17 Da by the molecular ion
and is typical of a hydroxyl group. In the same spectrum, the peak at m/z 16 could formally
correspond to ions CH4 •+ , O+ or even CH3 OH2+ , because they all have m/z values equal
to 16 at low resolution. However, O+ is unlikely to occur, and a doubly charged ion for
such a small molecule is not stable enough to be observed.
The atomic mass units u or Da have the same fundamental definition:
1 u = 1 Da = 1.660 540 × 10−27 kg ± 0.59 ppm
However, they are traditionally used in different contexts: when dealing with mean isotopic
masses, as generally used in stoichiometric calculations, Da will be preferred; in mass
spectrometry, masses referring to the main isotope of each element are used and expressed
in u.
There are different ways to define and thus to calculate the mass of an atom, molecule
or ion. For stoichiometric calculations chemists use the average mass calculated using
the atomic weight, which is the weighted average of the atomic masses of the different
isotopes of each element in the molecule. In mass spectrometry, the nominal mass or the
monoisotopic mass is generally used. The nominal mass is calculated using the mass of the
predominant isotope of each element rounded to the nearest integer value that corresponds
to the mass number, also called nucleon number. But the exact masses of isotopes are not
exact whole numbers. They differ weakly from the summed mass values of their constituent
particles that are protons, neutrons and electrons. These differences, which are called the
mass defects, are equivalent to the binding energy that holds these particles together.
Consequently, every isotope has a unique and characteristic mass defect. The monoisotopic
mass, which takes into account these mass defects, is calculated by using the exact mass of
the most abundant isotope for each constituent element.
The difference between the average mass, the nominal mass and the monoisotopic mass
can amount to several Da, depending on the number of atoms and their isotopic composi-
tion. The type of mass determined by mass spectrometry depends largely on the resolution
and accuracy of the analyser. Let us consider CH3 Cl as an example. Actually, chlorine
atoms are mixtures of two isotopes, whose exact masses are respectively 34.968 852 u
4 INTRODUCTION
and 36.965 903 u. Their relative abundances are 75.77 % and 24.23 %. The atomic weight
of chlorine atoms is the balanced average: (34.968 852 × 0.7577 + 36.965 903 × 0.2423)
= 35.453 Da. The average mass of CH3 Cl is 12.011 + (3 × 1.00 794) + 35.453 =
50.4878 Da, whereas its monoisotopic mass is 12.000 000 + (3 × 1.007 825) + 34.968 852 =
49.992 327 u. When the mass of CH3 Cl is measured with a mass spectrometer, two iso-
topic peaks will appear at their respective masses and relative abundances. Thus, two
mass-to-charge ratios will be observed with a mass spectrometer. The first peak will be
at m/z (34.968 852 + 12.000 000 + 3 × 1.007 825) = 49.992 327 Th, rounded to m/z 50.
The mass-to-charge value of the second peak will be (36.965 90 + 12.000 000 + 3 ×
1.007 825) = 51.989 365 Th, rounded to m/z 52. The abundance at this latter m/z value
is (24.23/75.77) = 0.3198, or 31.98 % of that observed at m/z 50. Carbon and hydrogen
also are composed of isotopes, but at much lower abundances. They are neglected for this
example.
For molecules of very high molecular weights, the differences between the different
masses can become notable. Let us consider two examples.
The first example is human insulin, a protein having the molecular formula
C257 H383 N65 O77 S6 . The nominal mass of insulin is 5801 u using the integer mass of
the most abundant isotope of each element, such as 12 u for carbon, 1u for hydro-
gen, 14 u for nitrogen, 16 u for oxygen and 32 u for sulfur. Its monoisotopic mass of
5803.6375 u is calculated using the exact masses of the predominant isotope of each element
such as C = 12.0000 u, H = 1.0079 u, N = 14.0031 u, O = 15.9949 u and S = 31.9721 u.
These values can be found in the tables of isotopes in Appendices 4A and 4B. Finally,
an average mass of 5807.6559 Da is calculated using the atomic weight for each ele-
ment, such as C = 12.011 Da, H = 1.0078 Da, N = 14.0067 Da, O = 15.9994 Da and S =
32.066 Da.
The second example is illustrated in Figure 2. The masses of two alkanes hav-
ing the molecular formulae C20 H42 and C100 H202 are calculated. For the smaller
alkane, its nominal mass is (20 × 12) + (42 × 1) = 282 u, its monoisotopic mass is
(20 × 12) + (42 × 1.007 825) = 282.3287 u rounded to 282.33 and its average mass is
(20 × 12.011) + (42 × 1.007 94) = 282.5535 Da. The differences between these differ-
ent types of masses are small but are more important for the heavier alkane. In-
deed, its nominal mass is (100 × 12) + (202 × 1) = 1402 u, its monoisotopic mass is
(100 × 12) + (202 × 1.007 825) = 1403.5807 u rounded to 1403.58 and its average mass
is (100 × 12.011) + (202 × 1.007 94) = 1404.7039 Da.
In conclusion, the monoisotopic mass is used when it is possible experimentally to
distinguish the isotopes, whereas the average mass is used when the isotopes are not
distinguishable. The use of nominal mass is not recommended and should only be used for
low-mass compounds containing only the elements C, H, N, O and S to avoid to making
mistakes.
Diagram of a Mass Spectrometer

A mass spectrometer always contains the following elements, as illustrated in Figure 3: a
sample inlet to introduce the compound that is analysed, for example a gas chromatograph
or a direct insertion probe; an ionization source to produce ions from the sample; one or
several mass analysers to separate the various ions; a detector to ‘count’ the ions emerging
HISTORY 5
Figure 2
Mass spectra of isotopic patterns of two alkanes having the molecular formulae C20 H42 and
C100 H202 , respectively. The monoisotopic mass is the lighter mass of the isotopic pattern
whereas the average mass, used by chemists in stoichiometric calculations, is the balanced
mean value of all the observed masses.
from the last analyser; and finally a data processing system that produces the mass spectrum
in a suitable form. However, some mass spectrometers combine the sample inlet and the
ionization source and others combine the mass analyser and the detector.
A mass spectrometer should always perform the following processes:
1. Produce ions from the sample in the ionization source.

2. Separate these ions according to their mass-to-charge ratio in the mass analyser.
3. Eventually, fragment the selected ions and analyze the fragments in a second analyser.
4. Detect the ions emerging from the last analyser and measure their abundance with the
detector that converts the ions into electrical signals.
5. Process the signals from the detector that are transmitted to the computer and control
the instrument through feedback.
History
A large number of mass spectrometers have been developed according to this fundamental
scheme since Thomson’s experiments in 1897. Listed here are some highlights of this
development [11, 12]:
1886: E. GOLDSTEIN discovers anode rays (positive gas-phase ions) in gas discharge
[13].
1897: J.J. THOMSON discovers the electron and determines its mass-to-charge ratio.
Nobel Prize in 1906.
6 INTRODUCTION
Figure 3
Basic diagram for
a mass spectrometer
with two analysers
and feedback control
carried out by a data
system.
1898: W. WIEN analyses anode rays by magnetic deflection and then establishes that
these rays carried a positive charge [14]. Nobel Prize in 1911.
1901: W. KAUFMANN analyses cathodic rays using parallel electric and magnetic fields
[15].
1909: R.A. MILLIKAN and H. FLETCHER determine the elementary unit of
charge.
1912: J.J. THOMSON constructs the first mass spectrometer (then called a parabola
spectrograph) [16]. He obtains mass spectra of O2 , N2 , CO, CO2 and COCl2 . He
observes negative and multiply charged ions. He discovers metastable ions. In 1913,
he discovers isotopes 20 and 22 of neon.
1918: A.J. DEMPSTER develops the electron ionization source and the first spectrometer
with a sector-shaped magnet (180◦ ) with direction focusing [17].
1919: F.W. ASTON develops the first mass spectrometer with velocity focusing [18].
Nobel Prize in 1922. He measures mass defects in 1923 [19].
1932: K.T. BAINBRIDGE proves the mass–energy equivalence postulated by Einstein
[20].
1934: R. CONRAD applies mass spectrometry to organic chemistry [21].
1934: W.R. SMYTHE, L.H. RUMBAUGH and S.S. WEST succeed in the first preparative
isotope separation [22].
HISTORY 7
1940: A.O. NIER isolates uranium-235 [23].

1942: The Consolidated Engineering Corporation builds the first commercial instrument
dedicated to organic analysis for the Atlantic Refinery Company.
1945: First recognition of the metastable peaks by J.A. HIPPLE and E.U. CONDON [24].
1948: A.E. CAMERON and D.F. EGGERS publish design and mass spectra for a lin-
ear time-of-flight (LTOF) mass spectrometer [25]. W. STEPHENS proposed the
concept of this analyser in 1946 [26].
1949: H. SOMMER, H.A. THOMAS and J.A. HIPPLE describe the first application in
mass spectrometry of ion cyclotron resonance (ICR) [27].
1952: Theories of quasi-equilibrium (QET) [28] and RRKM [29] explain the monomolec-
ular fragmentation of ions. R.A. MARCUS receives the Nobel Prize in 1992.
1952: E.G. JOHNSON and A.O. NIER develop double-focusing instruments [30].
1953: W. PAUL and H.S. STEINWEDEL describe the quadrupole analyser and the ion
trap or quistor in a patent [31]. W. PAUL, H.P. REINHARD and U. Von ZAHN, of
Bonn University, describe the quadrupole spectrometer in Zeitschrift für Physik in
1958. PAUL and DEHMELT receive the Nobel Prize in 1989 [32].
1955: W.L. WILEY and I.H. McLAREN of Bendix Corporation make key advances in
LTOF design [33].
1956: J. BEYNON shows the analytical usefulness of high-resolution and exact mass
determinations of the elementary composition of ions [34].
1956: First spectrometers coupled with a gas chromatograph by F.W. McLAFFERTY [35]
and R.S. GOHLKE [36].
1957: Kratos introduces the first commercial mass spectrometer with double focusing.
1958: Bendix introduces the first commercial LTOF instrument.
1966: M.S.B. MUNSON and F.H. FIELD discover chemical ionization (CI) [37].
1967: F.W. McLAFFERTY [38] and K.R. JENNINGS [39] introduce the collision-
induced dissociation (CID) procedure.
1968: Finnigan introduces the first commercial quadrupole mass spectrometer.
1968: First mass spectrometers coupled with data processing units.
1969: H.D. BECKEY demonstrates field desorption (FD) mass spectrometry of organic
molecules [40].
1972: V.I. KARATEV, B.A. MAMYRIM and D.V. SMIKK introduce the reflectron that
corrects the kinetic energy distribution of the ions in a TOF mass spectrometer [41].
1973: R.G. COOKS, J.H. BEYNON, R.M. CAPRIOLI and G.R. LESTER publish the
book Metastable Ions, a landmark in tandem mass spectrometry [42].
1974: E.C. HORNING, D.I. CARROLL, I. DZIDIC, K.D. HAEGELE, M.D. HORNING
and R.N. STILLWELL discover atmospheric pressure chemical ionization (APCI)
[43].
8 INTRODUCTION
1974: First spectrometers coupled with a high-performance liquid chromatograph by P.J.

ARPINO, M.A. BALDWIN and F.W. McLAFFERTY [44].
1974: M.D. COMISAROV and A.G. MARSHALL develop Fourier transformed ICR
(FTICR) mass spectrometry [45].
1975: First commercial gas chromatography/mass spectrometry (GC/MS) instruments
with capillary columns.
1976: R.D. MACFARLANE and D.F. TORGESSON introduce the plasma desorption
(PD) source [46].
1977: R.G. COOKS and T.L. KRUGER propose the kinetic method for thermochemical
determination based on measurement of the rates of competitive fragmentations of
cluster ions [47].
1978: R.A. YOST and C.G. ENKE build the first triple quadrupole mass spectrometer,
one of the most popular types of tandem instrument [48].
1978: Introduction of lamellar and high-field magnets.
1980: R.S. HOUK, V.A. FASSEL, G.D. FLESCH, A.L. GRAY and E. TAYLOR
demonstrate the potential of inductively coupled plasma (ICP) mass spectrometry
[49].
1981: M. BARBER, R.S. BORDOLI, R.D. SEDGWICK and A.H. TYLER describe the
fast atom bombardment (FAB) source [50].
1982: First complete spectrum of insulin (5750 Da) by FAB [51] and PD [52].
1982: Finnigan and Sciex introduce the first commercial triple quadrupole mass spec-
trometers.
1983: C.R. BLAKNEY and M.L. VESTAL describe the thermospray (TSP) [53].
1983: G.C. STAFFORD, P.E. KELLY, J.E. SYKA, W.E. REYNOLDS and J.F.J. TODD
describe the development of a gas chromatography detector based on an ion trap
and commercialized by Finnigan under the name Ion Trap [54].
1987: M. GUILHAUS [55] and A.F. DODONOV [56] describe the orthogonal ac-
celeration time-of-flight (oa-TOF) mass spectrometer. The concept of this tech-
nique was initially proposed in 1964 by G.J. O’Halloran of Bendix Corporation
[57].
1987: T. TANAKA [58] and M. KARAS, D. BACHMANN, U. BAHR and F. HIL-
LENKAMP [59] discover matrix-assisted laser desorption/ionization (MALDI).
TANAKA receives the Nobel Prize in 2002.
1987: R.D. SMITH describes the coupling of capillary electrophoresis (CE) with mass
spectrometry [60].
1988: J. FENN develops the electrospray (ESI) [61]. First spectra of proteins above
20 000 Da. He demonstrated the electrospray’s potential as a mass spectrometric
technique for small molecules in 1984 [62]. The concept of this source was proposed
in 1968 by M. DOLE [63]. FENN receives the Nobel Prize in 2002.
HISTORY 9
1991: V. KATTA and B.T. CHAIT [64] and B. GAMEN, Y.T. LI and J.D. HENION
[65] demonstrate that specific non-covalent complexes could be detected by mass
spectrometry.
1991: B. SPENGLER, D. KIRSCH and R. KAUFMANN obtain structural information
with reflectron TOF mass spectrometry (MALDI post-source decay) [66].
1993: R.K. JULIAN and R.G. COOKS develop broadband excitation of ions using the
stored-waveform inverse Fourier transform (SWIFT) [67].
1994: M. WILM and M. MANN describe the nanoelectrospray source (then called mi-
croelectrospray source) [68].
1999: A.A. MAKAROV describes a new type of mass analyser: the orbitrap. The orbitrap
is a high-performance ion trap using an electrostatic quadro-logarithmic field [5,69].
The progress of experimental methods and the refinements in instruments led to spectac-
ular improvements in resolution, sensitivity, mass range and accuracy. Resolution (m/δm)
developed as follows:
m/δm
1913 13 Thomson [16]
1918 100 Dempster [17]
1919 130 Aston [18]
1937 2000 Aston [70]
1998 8 000 000 Marshall and co-workers [71]
A continuous improvement has allowed analysis to reach detection limits at the pico-,
femto- and attomole levels [72, 73]. Furthermore, the direct coupling of chromatographic
techniques with mass spectrometry has improved these limits to the atto- and zeptomole
levels [74,75]. A sensitivity record obtained by mass spectrometry has been demonstrated by
using modified desorption/ionization on silicon DIOS method to measure concentration of a
peptide in solution. This technique has achieved a lower detection limit of 800 yoctomoles,
which corresponds to about 480 molecules [76].
Regarding the mass range, DNA ions of 108 Da were weighed by mass spectrometry
[77]. In the same way, non-covalent complexes with molecular weights up to 2.2 MDa were
measured by mass spectrometry [78]. Intact viral particles of tobacco mosaic virus with a
theoretical molecular weight of 40.5 MDa were analysed with an electrospray ionization
charge detection time-of-flight mass spectrometer [6].
The mass accuracy indicates the deviation of the instrument’s response between the
theoretical mass and the measured mass. It is usually expressed in parts per million
(ppm) or in 10−3 u for a given mass. The limit of accuracy in mass spectrometry is about
1 ppm. The measurement of the atomic masses has reached an accuracy of better than
10−9 u [79].
In another field, Litherland et al. [80] succeeded in determining a 14 C/12 C ratio of
1:1015 and hence in dating a 40 000-year-old sample with a 1 % error. A quantity of 14 C
corresponding to only 106 atoms was able to be detected in less than 1 mg of carbon
[81].
10 INTRODUCTION
Ion Free Path

All mass spectrometers must function under high vacuum (low pressure). This is neces-
sary to allow ions to reach the detector without undergoing collisions with other gaseous
molecules. Indeed, collisions would produce a deviation of the trajectory and the ion would
lose its charge against the walls of the instrument. On the other hand, ion–molecule colli-
sions could produce unwanted reactions and hence increase the complexity of the spectrum.
Nevertheless, we will see later that useful techniques use controlled collisions in specific
regions of a spectrometer.
According to the kinetic theory of gases, the mean free path L (in m) is given by
kT
L= √ (1)
2pσ
where k is the Boltzmann constant, T is the temperature (in K), p is the pressure (in Pa) and σ
is the collision cross-section (in m2 ); σ = π d2 where d is the sum of the radii of the stationary
molecule and the colliding ion (in m). In fact, one can approximate the mean free path of
an ion under normal conditions in a mass spectrometer (k = 1.38 × 10−21 J K−1 , T ≈ 300 K,
σ ≈ 45 × 10−20 m2 ) using either of the following equations where L is in centimetres and
pressure p is, respectively, in pascals or milliTorrs:
0.66
L= (2)
p
4.95
L= (3)
p
Table 1 is a conversion table for pressure units. In a mass spectrometer, the mean free path
should be at least 1 m and hence the maximum pressure should be 66 nbar. In instruments
using a high-voltage source, the pressure must be further reduced to prevent the occurrence
of discharges. In contrast, some trap-based instruments operate at higher pressure.
However, introducing a sample into a mass spectrometer requires the transfer of the
sample at atmospheric pressure into a region of high vacuum without compromising the
latter. In the same way, producing efficient ion–molecule collisions requires the mean free
path to be reduced to around 0.1 mm, implying at least a 60 Pa pressure in a region of the
Table 1 Pressure units. The official SI unit is

the pascal.
1 pascal (Pa) = 1 newton (N) per m2

1 bar = 106 dyn cm−2 = 105 Pa
1 millibar (mbar) = 10−3 bar = 102 Pa
1 microbar (µbar) = 10−6 bar = 10−1 Pa
1 nanobar (nbar) = 10−9 bar = 10−4 Pa
1 atmosphere (atm) = 1.013 bar = 101 308 Pa
1 Torr = 1 mmHg = 1.333 mbar = 133.3 Pa
1 psi = 1 pound per square inch = 0.07 atm
REFERENCES 11
spectrometer. These large differences in pressure are controlled with the help of an efficient
pumping system using mechanical pumps in conjunction with turbomolecular, diffusion or
cryogenic pumps. The mechanical pumps allow a vacuum of about 10−3 Torr to be obtained.
Once this vacuum is achieved, the operation of the other pumping systems allows a vacuum
as high as 10−10 Torr to be reached.
The sample must be introduced into the ionization source so that vacuum inside the
instrument remains unchanged. Samples are often introduced without compromising the
vacuum using direct infusion or direct insertion methods. For direct infusion, a capillary is
employed to introduce the sample as a gas or a solution. For direct insertion, the sample
is placed on a probe, a plate or a target that is then inserted into the source through a
vacuum interlock. For the sources that work at atmospheric pressure and are known as
atmospheric pressure ionization (API) sources, introduction of the sample is easy because
the complicated procedure for sample introduction into the high vacuum of the mass
spectrometer is removed.
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By means of the comparison with socialism, I have endeavoured to
emphasise that the woman movement’s formation of dogmas and its
doctrinary fanaticism are not effects of the peculiarity of the
feminine mind. These phenomena are typical of every movement of
the time thus far observed. They are essential above all because a
new belief without dogma and without ritual is for the masses a
sword without a hilt: it offers nothing tangible, nothing whereby the
masses can come into relation with the idea.
That certain feminists still believe that the woman movement has
advanced just as the exodus of the Children of Israel out of the land
of bondage, that is to say, under God’s special protection against
wandering astray; that they stigmatise as “treason” and “defection”
the assertion that this movement was determined by the same
psychological and sociological laws as every other movement for
freedom—this shows to how high a degree many leaders of the
woman movement lack elementary psychological and sociological
conceptions. This deficiency is, however, being continually remedied.
And in the generation which now advances, dogmatic fanaticism has
well nigh vanished, but pure enthusiasm is preserved.
We can thus expect from this generation a clearer understanding
of the necessary social repressions which the woman movement has
now sufficient strength to impose upon itself without forfeiting
thereby its character of a movement for freedom. As such it cannot
and dare not cease until it has attained all its ends. As long as the law
treats women as one race, men as another, there is a woman
question. Not until man and woman, equal and united, work together
for mankind will the woman movement belong to the past.
CHAPTER III
THE INFLUENCE OF THE WOMAN
QUESTION UPON SINGLE WOMEN
The following comparisons between the life of women, especially

their spiritual life of about fifty years ago and their life as it has
shaped itself under the influence of the woman movement, have been
arranged in descending scale. They begin with that phase of women’s
life in which this influence was most favourable from the point of
view of life enhancement, namely with the life of unmarried women.
You will find to-day, among women seventy or eighty years of age,
one or another type of that fine culture which the gifted single
woman, in comfortable circumstances, could attain in the previous
century. Her home, especially if it was an estate in the country,
became a cultural fireside which radiated light and heat for relatives
and friends. The lesser gifted disseminated, each according to her
nature, comfort or discomfort, yet could in extremity at least be sure
of the homage of their future heirs. Toward those dependent upon
them, these women were sometimes kind, sometimes indifferent,
sometimes hard: the feeling of social responsibility was an unknown
idea to them. The penniless single women, on the contrary, were
found either in one of the “respectable” positions which, however,
brought with them a multitude of humiliations: as governess,
companion, housekeeper—in Germany also as maid of honour at one
of the numerous small courts—or in some charitable institution for
gentle folks, an asylum for pauvres honteuses; but most frequently in
the corner of the home of a relative. This corner was at times the
warmest and most confidential in the whole house, that corner which
the children sought for stories and sweetmeats; the youth, to find an
embrace in which he could pour forth his grief, an ear which listened
to his most beautiful dreams. But it happened more frequently that
the “aunt” looked upon as a “necessary evil” was in reality that very
thing. Humiliated and embittered, she became ingenious in making
those about her suffer for her afflictions. Before they became
hopelessly old, the “aunts” were the laughing stock of the young
through their efforts, in the eleventh hour, to reach the “peaceful
haven of matrimony”; and they themselves looked with envious eyes
upon the good fortune of the young. We meet the unmarried woman
of that time at her best as trusty servant who shared the cares, the
joys, and the sorrows of the family and, in her garret chamber, of
which she could be certain to the day of her death, she looked back
upon a rich life lived vicariously. Not infrequently, she rejected a
marriage proposal in order to stay with her beloved master and
mistress to whom she knew she was indispensable. The superfluous
women previously mentioned would have thrown themselves into
the arms of Beelzebub had he come as suitor. When the years passed,
when neither their desire for activity nor the thirst of the heart nor of
the senses was quenched, then not infrequently insanity conjured up
for these lonely women a life-content for which they had longed in
vain. To-day, however, we have for the position which the
expression, “a forsaken old maid,” betokens an entirely new type:
“the glorified spinster,” as the joyous, active, independent unmarried
woman is called by the people among whom she first became a
reality. Among these women, independent through their work, useful
to society, that older type is still occasionally found perhaps, a
survival of the time when emancipation was rather generally
interpreted as freedom for masculinity. The “man-woman” in
masculine attire, with weapons of defence against man in one hand
and a cigarette in the other, her soul filled with mad ambition for her
own sex and, as representative of her entire sex, with hatred toward
the other, was however always rare. Now, she has almost entirely
vanished, except alas, the cigarette. But she smokes it now often with
—masculine friends! She follows in her mode of life, as in her dress,
the law of good taste—not to offend; she endeavours, if only with a
flower or two, to give a glimmer of cosy comfort to her place of work.
This comfort, which often comes into the public life with woman is
perhaps the reason why many men, who first looked with
indignation upon feminine fellow-workmen, would now miss them.
The more personal the culture of these women becomes, the more
they endeavour, according to their time and means, to express their
personality in the lines and colours of their dress and in the
arrangement of their room. Those best situated often succeed,
toward the end of their working days, in winning their own little
home which they perhaps share with a friend, or they join a co-
operative enterprise and can thus raise their standard of living. The
same women who, at twenty-five, scornfully declared that they
“would never bury their head in a sauce-pan,” are now, at fifty,
consciously aware of the significance of the table for the activity of
the brain; indeed they are now quite as proud if they have prepared a
good dish as they were in their youth when they passed a fine
examination!
It is not to be wondered at that the emancipated women, exactly as
all recently emancipated masculine classes and races, at first groped
insecurely after a new form. The astonishing thing, on the contrary,
is that women adapted themselves so quickly to the new
circumstances; that the transition period furnished so few grotesque
types; that the present shows so many harmonious types, each in her
own way. This harmony of single women is no mere form. It has its
inner counterpart in the satisfaction with their existence, an
existence in accord with their desires. The psychology was not
exhaustive which saw in feminism only a “spinster question,” a
question of the unmarried woman, springing from the surplus of
women and the increasing difficulty or disinclination of men to
contract marriage—a question therefore for the ugly, not for the
beautiful; for the unmarried, not for the married; for the poor, not
for the rich. For a great number of beautiful women prefer to remain
unmarried; a great number of rich desire to work; a great number of
married women are zealous suffragists. Fifty years ago, we saw the
most clever women idealise an ape into a god; now, the modern,
intelligent working girl, when she looks about her for her ideal,
exercises a lively criticism. She often flirts with one who exhibits
some phase of the ideal, but she has too clear an understanding and
too much to do to imagine a great feeling for one who is unworthy.
So it often happens that youth has passed without such a feeling
having stirred her. And she enters without deep regret the age when
ambition and desire for power become her life stimulants. From
these women of predominating mind and will is formed more and
more what Ferrero calls “The third sex,” Maudsley, “The sexless ant”:
energetic, clever, happy in their work, cool, but sound; in private life,
in the zeal of everyday work, often egoistic but willing to make
sacrifices in face of social exigencies.
So a great part of the fifty-year-old women form an exception since
they with true instinct have remained unmarried. For in the same
degree that their metallic being is well adapted to the machinery of
society, it is little qualified to make a home for husband and children.
They do not depreciate however the value of this task, unless they be
fanatic feminists. In that event they reproach the women who wish to
marry with “betraying the woman cause”; they demand at times, as
imperative loyalty toward this cause, that their friends shall protest
against the present marriage laws at least by the form of their
marriage alliance if not even by not marrying at all. Their theory of
equality has at times been carried so far that—as recently happened
in France—they advocate women’s performing also masculine
military service.
But in spite of their aridity and inflexibility of principle how much
more human are even these feminists than the “ill-natured” aunts of
earlier times who became ill-natured exactly because their
temperament was of the kind mentioned above, but who could find
no sphere of operation for their passionate longing for activity. One
or another was perhaps burning with ambition. For there are women
as well as men who can live only as pagan gods, in the blaze and
perfume of sacrificial fires. In their youth these ambitious natures
could be satisfied by triumphs in social life. But later the passion
became a fire in a powder cask and occasioned incessant explosions.
Now it is the electric motive power for an activity of general utility.
The “aunts” of the earlier time who felt themselves always
overlooked and injured are most easily recognised again in the
literary and artistic field to which daily bread or ambition now urges
many women, who endeavour to compensate by energetic work for
the talent which nature denied them. Since these women are
ordinarily not people of understanding but of feeling, they must in a
double sense be dissatisfied with a life which in addition is, in most
cases, still filled with economic cares and the humiliations arising
therefrom. And yet in spite of all, how much richer is their life to-day
than it would have been fifty years ago when they would have been
obliged to sit and draw their needles through interminable pieces of
handwork, after ugly patterns and for unnecessary uses, or to
compose sentimental birthday verses for persons whom they
abominated.
Yet there are always those women natures who, in the past, had
the qualifications for a real “dear aunt,” who gently calmed the
conflicts and filled the gaps in the home of which they had become
members. The most tender and sensitive of these modern women,
who, rain or shine, year in year out, hasten to and from a work
indifferent to them at heart, not infrequently breathe a sigh of
longing for those times when, as “aunts,” they could have received
and imparted warmth in a home. But then again there come
moments when they know how to value the independence which puts
them in a position to give help where otherwise there would be none;
when for example they can send a nephew to college, or a friend to a
sanatarium, or provide their mother with a nurse, which they
themselves can not be.
This kind of single woman fulfills more or less the office of family
provider just as she also is always ready with word and deed in
circles of friends and comrades. These women are so engrossed that
the time of love, sometimes love itself, passes them by without their
observing it. Their youth flees and they feel with sadness that their
woman’s life is unlived. But they persuade themselves that they have
had enough in their work, that many little joys can take the place of
great happiness. And they believe this as truly as the infant believes
he is satisfied when he sucks his own thumb. But some of these
women acknowledge perhaps, when they have passed the fifties, that
they were often tempted to call out to the first best man, “Give me a
child.” Sometimes it happens that in their last youth they appease
their mother longing by adopting a foster child; sometimes they still
this longing by a child of their own, from a love relation or a
marriage. This late and uncertain happiness is often made possible
exactly through their work. And then, if not earlier, they bless this
work which gives them the economic possibility, and thereby also the
courage, for this hazardous adventure.
More frequent than these are the cases however where single
women, who have passed their first youth, find in friendship for
another woman a valve for their, in great part, unused feelings. In
some natures this friendship will be jealous and exacting, in others
true and devoted. I wish to emphasise that I speak here of entirely
natural spiritual conditions. There is to-day much talk about
“Sapphic” women; and it is even possible that they exist in that
impure form which men imagine. I have never met them,
presumably because we rarely meet in life those with whom no fibre
of our being has any affinity. But I have often observed that the
spiritually refined women of our time, just as formerly the spiritually
refined men of Hellas, find most easily in their own sex the qualities
which set their spiritual life in the finest vibration of admiration,
inspiration, sympathy and adoration.
The fundamental types of single women depicted here—the person

of intellect and the person of feeling—are found everywhere. The
former according to current opinion already predominate in
America; in Europe, it seems to me, the latter still prevail. That the
main classes include innumerable varieties, it is needless to say.
There are for example the numerous, quite ordinary, family girls who
would be happy if they could give up their independence in order to
enjoy the protection of their parents’ or their own home. And the
same obtains also with the quite as ancient type of woman, Undine,
who—soulless and cold—enslaves all men. If she is in any civic
vocation, she knows how to get the smallest amount of work for
herself and, in case she is engaged in the artistic field, the best
possible criticism. Conscience is an acquaintance which she has
never made and she is also of the opinion that everything agreeable
is permitted to her; she simply slides past anything disagreeable.
Although work belongs to these disagreeable things, she continues it
until she has found means to place her “qualities” in the most
advantageous manner upon the matrimonial market.
The diametrical antithesis of this curvilinear type is the rectilinear.
It has, just as the preceding type, existed at all times. It is the woman
who really never demanded anything of life but “a work and a duty”
and finds both in abundance in all positions of life. She is found year
in year out at her desk, in appropriate working garb, free from all
æsthetics; proud “if she never has needed to miss a day”; proud that
she never has come late. On the contrary she never goes on time. For
she has so grown into the business or the office that she takes
everything upon herself that is required without murmuring, as a
well-disciplined soldier in the ranks of the grey working army;
thankful, in addition, if her long working cares yield her a little life
annuity or pension for her old age. This type is found principally
among women over fifty—fortunately. For this class of women which
the pre-feministic circumstances created, have, by their “frugality”
carried almost to the verge of criminality, by their humble,
conscientious servitude, lowered the wages of their colleagues who
are more full of life. These latter have begun work in the hope that it
finally will “free” them; that is, will give them something of that for
which their innermost being longs, not only their daily bread—a
bread which sickness or a turn of affairs moreover can take from
them at any time. And perhaps they never succeed even in having
their own room where they at least could have repose! Underpaid,
overworked, tired to death, who can wonder if these women have
lost, if they ever possessed them, the essential characteristics of
“womanhood”—active kindness, repose even in movement, charming
gentleness? The Icelandic poet of yore already knew that “Few
become fair through wounds.” These women must put all their
strength into their work and into the effort to conceal their
underpayment by “respectable” clothing, or else lose their positions.
In everything else they must economise to the utmost and perhaps in
addition be laughed at because of their economy. They succeed, often
admirably, in maintaining themselves in proud fair struggle, in
rejecting “erotic” perquisites to add to their income and in fulfilling
conscientiously the requirements of their work. Yet to do this with
lively interest, with preserved spiritual elasticity, with quiet
amiability—for this their strength does not suffice, exhausted by
insufficient nourishment, insufficient sleep, still more insufficient
recreation, and strained daily to the utmost. Their nervousness finds
vent in either hard or hysterical expression and the public, annoyed
by their ill-humour, divines little of the tragedies enacted in offices,
business houses, cafés or similar places. If a suicide concludes the
tragedy, the public shudders for a moment and—all goes on as
before.
Thus “emancipation” presents itself in reality for millions of
women. To what extent the middle-class woman movement is
indirectly to blame for this fact has already been emphasised.
The essential reason is however the prevailing economic condition
of society. By the uninterrupted fever of competition and the
accumulation of riches, it dries up the soul and robs it of goodness as
well as of joy. When the great, beautiful, eternal sources of joy are
exhausted, the life stimulus is sought in exclusively physical
pleasures, which are always made more exciting in order to be able to
arouse still, in the languid nervous system, feelings of desire.
Moreover, there is the neurosis and weariness of life of the
overworked, of those continually quaking about their material safety,
of those who could be revived by the noble and simple joys of life, to
which those jaded with riches are already not susceptible; but for all
these millions and millions such joys are not accessible because
hunger for profit depresses wages. If in addition to that we take into
account the increasing suffering of the best because of the ever
developing feeling of solidarity; and if finally we consider that
women, who through the protection of the home could preserve
something of warmth-irradiating energy, are now in increasing
numbers driven out of the home, then we have some of the reasons
which—in higher degree than the religious and philosophic reasons
which also exist—contribute to the joylessness of our time.
A contribution to the meagre stock of good fortune of the present

time is furnished however by the joy of life among young girls
working under favourable conditions. Among them we meet a new
soul condition, which could be designated, as briefly as possible, as
covetousness of everything which can promote their personal
development and a beautiful liberality with what is thus won. They
can gratify their energetic desire for self-development by sport,
travel, books, art and other means of culture; their freedom of action
between working hours is not restricted by private duties. They can
utilise their leisure time and their income as they please: for
recreation, pleasure, social intercourse, social work or private,
charitable activity. No father nor husband encroaches upon their free
agency. And so dear does this liberty become to them through the
manifold joys which it furnishes, that these young girls, in constantly
increasing numbers, refuse to relinquish their individual
independence for the sake of a marriage which, even presupposing
the happiest love, always means a restriction of the freedom of
movement that they enjoyed while single. And since the modern
woman knows that, in the sphere of spiritual values, nothing can be
attained without sacrifice, she prefers to keep free agency and to
sacrifice love. If she chooses in the opposite direction, the task of
adaptation will be the more difficult, the longer and the more
intensely she has enjoyed freedom. The modern young girl, if she
deigns to bestow her hand upon a man, not infrequently has her
pretty head so crammed full of principles of equality that she
sometimes (frequently in America), by written contract establishes
her independence to the smallest detail, which sometimes includes
separate apartments and the prohibition that either of the
contracting parties shall have the key to the apartment of the other.
There are many varieties of the new type of woman. There is for
instance the tom-boy, the “gamin,” who for her life cannot give up
the right to mad pranks and mischievous jokes. There is the girl
consumed with ambition, who sacrifices all other values in order to
attain the goal of her ambition in art or science. There is the
fanatically altruistic girl, who considers the work for mankind so
important that she feels she has not the right to an “egoistic” love
happiness. There is the ascetic ethereal girl, who looks upon
marriage and child-bearing as animal functions, unworthy of a
spiritual being, but above all as unbeautiful. And for many of these
modern, æsthetically refined, nervously sensitive young girls the
æsthetic point of view is decisive. All love the work which permits
them to live according to their ideals. Still it often happens that
Ovidian metamorphoses take place: that the young girl sees the cloud
or the swan transformed into a god, upon whose altar she sacrifices,
with joy, her free agency and everything else which only a few weeks
earlier she cherished as her holy of holies. The men who view this
process with a smile, think that the anti-erotic ideals were only a new
weapon of defence in the eternal war between the sexes. But these
men often learn how mistaken they were when they themselves
become participators in the war. They meet women so proud, so
sensitive regarding their independence, so merciless in their
strength, so easily wounded in their instincts, so zealous to devote
themselves to their personal task, so determined to preserve their
freedom, that erotic harmony seldom can be realised. Yes, these
women often repudiate love only because it becomes a bond to their
freedom, a hindrance to their work, a force for the bending of their
will to another’s will.
The women, womanly in their innermost depths, who really feel
free only when they give themselves wholly, are becoming
continually more rare. But where such a wholly devoted woman still
exists, she is the highest type of woman which any period has
produced. Especially if she springs from a family of old culture. She
has then, combined in her personality, the best of tradition and the
best of the revolution evoked by the woman movement. The fibres of
her being absorb their nourishment with instinctive certainty out of
the fruitful soil which pride, devotion to duty, family love,
requirements of culture and refinement of form, for many
generations, have created. But her conscious soul-life flowers in the
sun of the present; she thinks new thoughts and has new aims. Just
as little as she disavows her desire for love, so little does she desire
love under other conditions than those of spiritual unity and human
equality. If she meets the man who can give her this and if she loves
him, then he can be more certain than the man of any other time that
he is really loved, that no ulterior motive obscures the devotion of
this free woman. He has seen her susceptible to all the riches of life;
has seen her assist in social tasks, perform the duty of every day
joyful in her work, proud of her independence attained through her
work. He knows that just as she is she would have continued to be if
he had not entered into her life. How different is this girl from the
one of earlier times, who was driven by the emptiness of her life into
continual love affairs, which could not lead to a marriage nor exist in
a marriage that possessed nothing of love!
This most beautiful new type of woman approaches spiritually the
aforementioned type of single, aged women, who because of their
economic independence found time for a fine personal culture. These
followed not infrequently in their youth, from a distance it is true,
but with joyous sympathy, the progress of the woman movement.
They shook their heads later over its extremes. With new joy they
regard the young girls just described, in whom they find a more
universal development than in themselves, because these young girls
have been developed through active consumption of power which
was spared to the older women, although they must have summoned
much passive energy in order to maintain their personality against
convention. The young girls find often in these older women a fine
understanding, which they richly reciprocate. Such terms of
friendship are the most beautiful which the present has to offer: they
resemble the meeting of the morning and evening red in the bright
midsummer nights of the North.
No time could have been so rich in exquisite feminine
personalities, at all ages and in all stages of life, as ours. We must not
draw our conclusions regarding the abundance of such women, in
the older culture epochs, from the illustrious names of women which
incessantly recur in the pictures of the earlier times—like stage
soldiers—until they give the illusion of a great host.
But exquisite women are even to-day exceptional. The Martha type
rather than the Mary type predominates. This is due on one hand to
decreasing piety, on the other hand to the kind of working and
society life. Fifty years ago single women were often spiritually
petrified, now more often they cannot succeed in settling into any
form. Their existence, turned outwardly, widens their sphere of
interest but makes their soul-life shallow. Restlessness is most
unfavourable to the “development of the personality,” which was
however the goal of the emancipation of woman. This development is
delayed most of all perhaps by the lack of personal contact with other
personalities, of immediate, intimate human connections. This can,
from no point of view, be supplied by the society or club life in which
single women are to-day absorbed.
CHAPTER IV
MOVEMENT UPON THE DAUGHTERS
As late as sixty or seventy years ago, the daughters of good families

had still few points of contact with life outside the four walls of the
home. From the hands of nurse-maids they went into those of the
governess, and after confirmation, studies were at an end. If it was a
cultured home then reading aloud or music was often practised,
whereby it is true no “specific education” qualifying them for
examinations was attained, but frequently a fine universal human
culture. There was always employment in the house for the zeal for
work. The great presses were filled with linen which was not
infrequently spun and woven by the daughters; in the autumn they
assembled for sausage-making and candle dipping; later, for
Christmas baking and roasting; in summer endless rows of glasses of
preserves were set in the store-room. Before Christmas, night after
night, Christmas presents were made; after Christmas, night after
night, they danced. At these balls those in outer respects uncomely,
received a foretaste of that waiting which must fill their life for many
long years: would the invitation to the dance—or the wooing
respectively—come or not? Every man whose shadow merely fell
upon the scene, was immediately considered from the point of view
of a suitor. As the years went by the girl, who before twenty-five
years of age was considered an “old maid,” saw how the glance of the
father and the brothers became gloomy, yes, she could even hear how
“unfortunate” she was. If such a daughter lived in a home poor in
books—and most of them were—then she could not even procure a
book she wished. For the daughters worked year in year out without
wages, in case they did not receive meagrely doled out pin-money
which only through great ingenuity sufficed for their toilette. All year
long there were christenings and birthday celebrations; in summer
games were played, where it was possible riding parties arranged, in
winter sleighing parties were organised. Other physical exercise was
considered superfluous. The young girls were averse to going to a
neighbouring estate if it lay a mile away; and during the week to take
a long walk for pleasure or sit down with a book, which had been
borrowed, would be considered simply as idling away one’s time. In
summer a cold bath was permissible—a warm bath was used only in
cases of sickness—but swimming was considered so unwomanly, that
whoever had learned it must keep it secret. Rowing, tobogganing and
skating were, even if permitted in the country, yet half in discredit as
“masculine.”
When grandfather related an heroic deed of some ancestress
whose proud countenance shone out among the family portraits,
then the daughter of such a family must have asked herself why this
deed was lauded while everything “manly” was forbidden her.
The days and years went by at the embroidery frame or netting
needles, amid continuous chatter about the family and neighbours,
amid eternal friction and in disputing back and forth over mere
trifles. The confined nervous force sought an outlet, and in an
existence where each one—according to the first paragraph of family
rights—interfered in the greatest as in the smallest concerns of all the
others, there was always plenty of material about which to become
irritated and excited.
In the country, life was, however, fuller and fresher than in the city
where the young girl had less to do and never dared go out alone;
yes, where a walk was considered so superfluous, that the mother of
the great Swedish feminist Fredrika Bremer advised her daughters to
jump up and down behind a chair when they insisted that they
needed exercise!
The relation to the parents, even if the principle of unswerving and

mute obedience was not wholly carried out, was ordinarily a
reverential alienation. Neither side knew the inner life of the other.
The temperament of the mother determined the everyday domestic
comforts, the will of the father the external occurrences of life, from
the trip to the ball to marriage. The daughter whose inclination
corresponded with the will of the father considered herself fortunate.
The one married against her will wept, but obeyed. As an almost
fabulous occurrence it was related of one or another girl that she
dared to say “No” before the marriage altar; cases were not unusual
in which daughters received a box on the ear and were confined to
their room until they accepted the bridegroom whom the father had
chosen. Even if a mother, moved by the recollections of her own
youth, attempted to support a daughter it rarely succeeded. For the
power of the father rested quite as heavily upon the wife. But the
worst however was to water myrtle year after year, without ever
being able to cut it for a bridal wreath. Even she, who in her heart
loved another, found it therefore often wisest to give her consent to
an acceptable suitor. Only the one whose dowry was valued at a “ton
of gold”—or who also was a celebrated beauty—could run the risk of
declining a courtship; yes, she could permit herself to occasion it
only to decline it. The more suitors she could recount, the prouder
she was; such a beauty even embroidered around her bridal gown the
monograms of all her earlier wooers.
The unmarried remained behind in an environment where the idea
prevailed that “woman’s politics are her toilettes, her republic is her
household and literature belongs to her trinkets.” The talented
daughter sewed the fine starched shirts in which her stupid brother
went to the academy and sighed therewith: “Ah, if one only were a
man.”
When the income of the house was small, she increased it perhaps
by embroidery, sold in deepest secrecy; for it was a disgrace for a girl
of good family to work for money. For her rebellious thoughts she
had perhaps a girl friend to whom she could pour out her heart—or a
sister. But it often fared with sisters growing old together, just as it
must fare with North-pole explorers wintering together, that those
holding together of necessity finally loathe one another from the
bottom of their hearts. And yet the sisters were most fortunate who
could grow old and die in their childhood home and were not
compelled to become old household fixtures in the home of relatives.
Not infrequently this last fate was their portion because a father, a
brother or a guardian out of personal, economical self-interest
prevented their marriage, or a brother through debt or studies had
defrauded them of their inheritance.
It was not the woman movement but the religious movement,
beginning among the Northern peoples almost simultaneously with
it, called in Sweden “Läseri” (“Reading”) that was the first spiritual
emancipation for the old or young unmarried girls—likewise for
wives who longed for a deeper content. Because they took seriously
the Bible doctrine that one should disregard the commands of the
family in order to follow Christ, the home gradually became
accustomed to one of the feminine members’ going her own way.
Often amid great struggles. For the “Reader” was more or less
considered as insane; the father was ashamed of her, the mother
mourned over her, the brothers laughed at her. But nothing could
hinder those strong in their faith from following the inner voice. And
so these women, without knowing it themselves, were a bridge to
that emancipation of women to which they themselves later—Bible in
hand—were often an obstacle.
The movement could not however be prevented. And now—how is

it now in the family? Already the ten-year-old talks about what she is
sometime going to be. Now, the sisters go with the brothers to school
or to the academy and share their intellectual interests as well as
their life of sport. Now, the fathers and mothers sit at home often
alone, for the daughters belong to that host of self-supporting girls
who can gratify the parents by short visits only. Alas, these visits are
not always an unclouded joy. There are collisions between the old
and the young often over seeming bagatelles. But a feather shows
which way the wind blows and the parents observe that, in the
spiritual being of the daughter, the wind blows from an entirely
different direction from theirs. The daughter, on the other hand,
thinks that perfect calm prevails in the being of her parents; she
wishes to raise the dust. The mother pleads her cause in dry and
offended manner, the daughter in superior and impetuous words.
Accustomed to her freedom, she encounters again at home control
over her commissions and omissions, attempts upon her privacy
from which she had been freed by leaving home. And they separate
again each with a sigh that they “have had so little of one another.” In
other cases—when the parents have followed the times and the
daughters understand that not only children but also parents must
be educated with tenderness—then the visits to the parents’ home
become on both sides elevating episodes in their lives. The daughters
repose in the parental tenderness, which they have only now learned
to value when they compare it with their customary loneliness. The
parents confide to the daughter their cares which she sometimes can
effectively lighten, and they revive with her spiritual interests which
they themselves had to lay aside. Through her own working life the
daughter has gained an entirely new respect for her parents. Through
her independence of parental authority she has now gained a
frankness, which makes a real interchange of ideas possible. They
discover that they can have something reciprocal for one another.
The father, who perhaps at first sighed when the young faces
vanished out of the home, now admits that it would have been
foolish if the whole troop of girls had continued here at home and so
had stood there at his demise, empty-handed, without professional
training. The mother, who had helped them persuade the father,
smiles, when he insists that he “would not exchange his capable girls
for boys.” And he is not at all afraid that the daughters could not
marry if they would; he remembered indeed how his contemporaries
declared that they “would never look at a girl student, a Blue
stocking,” and yet so many of these were now happily married to—
girl students.
Beside these results of the independence of the daughters which
elevate life for all sides, there are opposite cases; when, for example,
a single daughter without outer economic compulsion or inner
personal necessity, impelled only by the current of the time, leaves a
home where her contribution of work could be significant, in order to
follow a vocation outside. The results are often of doubtful value, not
only from a social point of view but also from that of the family and
herself, when the daughter remains at home but carries on a work
outside. This comes partly because they are contented with less pay
and thus lower the wages of those who support themselves entirely;
partly because they over-exert themselves. In those cases where
several daughters can share with one another the domestic duties, no
over-exertion results perhaps. But when a single daughter combines
an exacting professional work with quite as exacting household
duties, then she is exhausted by her double task; then she feels the
burden, not the joy, of work. For all professional working girls who
remain at home, have moreover in addition, even under the most
favorable circumstances, the spiritual strain of turning from work
back again to the gregarious demands of the home, as well as to the
many different attractions and repulsions, antipathies and
sympathies which determine the deviations in temperature of the
home; the strain of respecting the sensibilities which must be spared
or of paying attention to the domestic demands which must be
refused, if the work is not to suffer from lack of rest and time for
preparation. All this can be so nerve racking that the young girl is
seized with an irresistible longing for a little home of her own, where
she would be mistress of her leisure time, and could see her own
friends—not alone those of her family,—where she could join those
who held the same views, where she, in a word, would live her life
according to the dictates of her personal demands. If she can, she
often does this. For to-day young girls live to apply the principle of
the woman movement—individualism. The older women’s rights
advocates desired, it is true, that woman should be allowed to
“develop her gifts,” but she should “administer” them for the benefit
of others; they desired that she should receive new rights from law
and custom, but that she should seek always in law and custom
support and security for her action. The young women’s rights
advocates, on the other hand, believe that their own growth, just as
that of animals and trees, is intended above all for self-development,
that in their own character the direction for their growth is specified,
and that they have not the right to confine themselves by
circumstances or subject themselves to influences by which they
know they hinder the development of their powers, according to
their individual natures. The more refined the feeling of personality
becomes, the more exactly these young people understand how to
choose what is essential for them and to repudiate what is a
hindrance. But before they attain this certainty they evince often an
unnecessary lack of consideration, and the family is often right when
it speaks of the egoism of youth. They find no opportunity for helping
father or mother nor for participation in the elders’ interests. The
whole family is rarely assembled even at meal-time; the daughters as
well as the sons rush off to lectures, work, sport, clubs. The mother
who sees how occupied the daughters are has not the heart to add to
their work or to thwart them in their pleasures; thus she allows the
selfishness of the young creatures to increase to the point where she
herself in indignation begins—seasonably and unseasonably—to
react against it. The young girl answers her mother’s reproof then
with the complaint that, “Mamma does not understand” her and that
she is “behind her time.” Especially the young examination-
champions distinguish themselves by their arrogance in the family as
in the club, where they look down upon the older ladies who have not
passed examinations just as they do upon their own mother.
It fares best in the families, and they are even now numerous,
where the mother herself has studied or worked outside the home
and therefore knows what domestic services she may or may not
require; where she herself personally understands the intellectual
occupation of the young people and has preserved her own
youthfulness, so that she becomes not infrequently the real friend of
her daughters and sons. If the mother, on the contrary, was one of
the many who, at the beginning of the woman movement, sacrificed
her own talent to the wishes of her family or the demands of the
home, in spite of the possibilities for its development made
accessible to her at that time, then she has often absolutely no
comprehension of the egoism of her daughter. She herself had acted
so entirely differently! Or she understands fully that in her daughters
as well as in her sons she views the attainment of a new conception of
life, with all its Storm and Stress, which the spring-times in the life of
mankind bring with them—an attainment in which, to her sorrow,
she could not take part in her youth.
At such spring-times youth is not, as the parents hoped, sunlight
and the twittering of birds in the home; but March storms and April
clouds. The parents feel themselves at first swept out, superfluous,
disillusioned. They are angered but rejuvenated, thanks to all the
new points of view that youth makes valid. Yes, father and mother
sometimes could live through a second youth if their own
contemporaries did not depress their buoyancy by their disapproving
astonishment and the children by their cool rejection of the
comradeship of their parents. But in spite of this twofold opposition,
there are now fathers and mothers who are able to enjoy the riches of
life quite as youthfully as and more deeply than their children; while
the parents of earlier times, especially the mother, forever stagnated
as early as forty. More and more frequently we find mothers who,
like their daughters, lead a spiritually rich and emotional life, who
have so preserved their physical youthfulness and who possess
moreover through experience and self-culture so refined a soul-life,
that, in regard to the impression they make, they are not infrequently
the rivals of their daughters. They are already revelations of that type
of woman which, in token of emancipation, has found the
equilibrium between the old devoted ideal and the new self-assertive
ideal. They view life from a height which gives them a survey also
over the essential, in questions concerning their own children. Even
if these become something other than the mothers wish, these
mothers are so penetrated with the idea of individualism that they let
the children follow their own course.
Modern fathers rarely find so happy a home as it once could be
with a bevy of daughters always at hand. But they find the home
richer in content, often also freer from petty dissensions. For in the
measure in which each member of the family desires his right and
his freedom, do all gradually learn to respect those of others. If the
parents consider with dignity their right and their freedom, then a
reciprocal consideration results after the boldness which youth
evinces under the first influence of the intoxication of freedom.
Youth, at first so proud and strong in their assurance of bringing new
ideal values to life, begin themselves to experience how the world
treats these; and what they once called their parents’ prejudice
appears to them now often in a new light. Their self-assertion
becomes a product of culture, out of a raw material. The
manifestations of their individualism become continually more
discreet, more controlled, but at the same time more essential and
more effective. When then the young people have found their way
and the parents endeavour to turn them aside to the main road—
which they call the way of wisdom or of duty—then certainly and
with right the young people put themselves on the defensive.
Even a devoted daughter cannot bring to the home to-day as
undivided a heart as formerly. But this gift was earlier a matter of
course, so to speak, a natural result of the conditions. But if to-day a
girl sacrifices a talent to filial duty, then it is an infinitely greater
personal sacrifice; a real choice. And if she does not make the
sacrifice, it is not in the least always on the ground of egoism. It
happens often in conviction that the unconditional demand of
Christianity that the strong must have consideration for the weak,
makes these latter often egoists and tyrants; that the strong, who are
more significant for the whole, are thus rendered inefficient.
If a troop of athletic boys continually conformed to the level of the
weakest, then all would remain upon a lower plane, and the weak
find no incentive to seek their triumphs in another sphere.
On the other hand it is fine and eminently sane and in harmony
with the laws of spiritual growth, when the strong shall help the weak
to reach a goal which is thus, in his own peculiar direction, really
attainable by him. Neither paganism nor Christianity has created the
most beautiful strength; it is a union of both. It has found its most
perfect expression in art in Donatello’s St. George, in Michelangelo’s
David: youths, whose victorious power conceals compassion and
whose compassion embraces even the conquered: symbols of
strength which has become kind, of kindness which has become
strong. If a mother has seen this expression upon the face of her son
or her daughter then she can address to life the words of Simeon:
“Now let thy servant depart in peace for mine eyes have seen thy
glory.” For the glory of life is the harmony between its two
fundamental powers—conquest and devotion: self-assertion and self-
sacrifice. In every new phase of the ethical development of mankind
the cultural problem is this harmony and the cultural profit is not the
per-dominance of one of the two but the perfected synthesis of both.
This problem has now become actual, through the woman
movement, for the feminine half of mankind, after the unconditional
spirit of sacrifice has obtained for centuries as the indispensable
attribute of womanliness. In the first stage of the woman movement
the majority of the “emancipated” were still determined by their
spirit of sacrifice, which they aspired to combine with their outside
professional work. This generation lived beyond its strength. The
younger generation of to-day does not believe that God gives
unlimited strength. For they have seen that those who live
unceasingly beyond their strength finally have no strength left, either
for others or for themselves. And they know that in the long run one
can live only upon his own resources and these must be conserved
and renewed in order to suffice. But this knowledge makes the
problem, which in the course of days and years appears in manifold
different forms, only more difficult of solution: the problem to find
the right choice in the collision between family duties, duties toward
oneself and duties toward society; the choice which shall bring with
it the essential enhancement of life.
The conflict is thus solved by some feminists: everything called
family ties and family feeling is referred to the “impersonal”
instinctive life, while our “personality” expresses itself in intellectual
activity, in study, in creation, in universally human ends, in social
activity, etc. And since the principle of emancipation is certainly the
freeing of the “personality,” it follows from this idea, in connection
with this definition of the personality, that the liberated personality
must place the obligations of the intellectual life absolutely above
those of the family life; the outside professional work above the work
in the home. In a word, the earlier definition of womanliness ignored
the universal human element, the present definition of personality
ignores the womanly element in woman’s being. The last solution of
the problem is quite as one-sided as the first.
The “principle of personality,” as it has just been described is
entertained especially in America. In Europe there are still women
who reflect deeply upon their own being and—who have a depth over
which they may meditate! These women have not yet succeeded in
simplifying the problem which is the central one of their life. They
know that not only do instincts, impulses of the will, feelings, form
the strongest part of the individual character which nature has given
them, but also that this part determines their thinking and creating
power—their whole conscious existence. They know that their
character receives its peculiarities through the development which
they themselves accord to one or another side of their individual
temperament. In one personality the intellectual life will
predominate, in another the emotional: in one the ethical, in another
the æsthetic motive. The personality becomes harmonious only when
no essential motive is lacking, when all attain a certain degree of
development, a harmony which is as yet only so won that no motive
receives its greatest possible development. Such a harmony has long
been the especial characteristic of the most beautiful womanhood,
while the most significant men have ordinarily achieved their
superior strength in one direction, at the cost of harmony in the
whole. If now women believe that they can achieve the strength of
men without, for that reason, being obliged to sacrifice something of
their harmony, then they believe their sex capable of possibilities
which thus far have been granted rarely and then only to the
exceptional in both sexes. What experience shows is: the greater
harmony of single women in a limited existence as compared with
the lack of harmony in the lives of daughters, owing to the
irreconcilable problems which their richer existence brings with it.
For these problems must be solved, at one time, by sacrifice of
intellectual, at another, by sacrifice of emotional values. In every
case, the sacrifice leaves behind it, not the joyful peace of fulfilled
duty, but the gnawing unrest of a duty still ever unfulfilled. Every
woman who has a heart knows it is at least quite as important a part
of her personality as her passion for science perhaps. If for example
she is obliged to surrender to another the loving service of a sick
father in order to pursue scientific researches, then her heart is quite
as certainly in the sick-room as, in case of the opposite choice, her
thoughts would have been in the laboratory. By calling one factor
“instinct” and the other “personality,” nothing is in reality gained.
Theorising ladies can easily write—the paper is forbearing. But
human nature is of flesh and blood. And therefore thousands of
women grapple to-day with tormenting questions:—When we women
shall belong entirely to industrial work and to the social life, who
then is left for the work of love? Only paid hands. What becomes
then of the warmth in human life when such a division of labour is
established that kindness becomes a profession, and the rest of us
shall be exempt from its practice because our “Personality” has more
important fields for the exercise of its strength? What does it signify
to live for society when we come to the service of society with chilled
hearts? If the warmth is to be preserved then we must have leisure
for love in private life, a right to love, peace and means for love. Only
thus can our hearts remain warm for the social life. Can the whole
really profit if we sacrifice unconditionally that part of the whole
which is nearest us? Can our feeling of solidarity increase toward
mankind when we pass by exactly those people to whom we could, by
our deeds, really show our sympathetic fellow-feeling?
The woman whose instinct life is still strong and sound, whose
personality has its roots deep in life—which means not social life
alone—she also understands how to determine what life in its
deepest import purposes with her; she knows how she serves it best,
whether by remaining in a position where she fulfils her personal
obligations as part of a family or by seeking another position where
she fulfils this obligation as a member of society.
It is true the erroneous idea still prevails in many homes that the
daughter must willingly sacrifice her social task for the family, a
sacrifice which the family would never even wish on the part of a son.
But the assurance that the daughter could have made another choice
instils in the family, unconsciously, a new conception of her sacrifice,
and gives to herself the courage to assume a position in the home
other than that she held at the time when no choice remained to her.
If the total of efficacious daughterly love of to-day and earlier times
be estimated, this total would not prove less now. But it is now given
rather in a great sum; earlier, on the contrary, in many small coins.
Because of the professional work of the daughter, there are now often
lacking in the home the ready obliging young hands whose help
father and brother so willingly engrossed; the cheerful comforter, the
admiring listener. But in a great hour the daughter or sister gives
now often a hundred times more in deep, personal understanding.
One draws a false conclusion when one thinks that the more closely a
family holds together the more it signifies a corresponding unity and
devotion. The young act in submission because they permit
themselves to be cowed by the family authority which like a steam-
roller passed over their wills and their hearts. But the indignation
that they experienced in their innermost hearts, the criticism which
they exercised among one another, were not less bitter than that
which they to-day openly utter.
The home life of fifty years ago was a school of diplomacy; it
especially served to oppose cunning to the father’s authority, and the
mother often taught the children to use this weapon of weakness.
Now the father does not wish to make himself ridiculous by saying: “I
forbid you,” for the daughter answers: “Well, then, I will wait until I
am twenty-one.” The threat, “I disinherit you,” recoils from the
determination of the daughter, “I can work.” Only in a distant
province, in a little town, or among the “upper ten thousand” of a
large city, where the daughters still often receive a “general
education,” which does not fit them to earn their living, are they
occupied all day without the feeling of having worked. They serve at
five o’clock teas, embroider for charity bazaars, etc. But they also
experience the power of the spirit of the time strongly enough to
know that they lead a selfish life but not a life of self. The lower the
scale of riches the more housework do the daughters have to
perform. But as a result of the patriarchal organisation of labour they
still perform this without their own responsibility, without the joy of
independence, without regular unoccupied time and without one
penny at their disposal!
Even in these circles however the spirit of the time is active; such a
daughter leads now in every case a life of much richer content than
some decades ago, when even though middle-aged she was still
treated as ignorant innocence and must allow herself to be extolled
to every possible marriage candidate. She suffers when she sees her
mother as the submissive wife, whose continual according smile has
graven lines of humility about her mouth, whose continually
pacifying tone has made her voice whining. She suffers when the
father cuts short a diversity of opinion with the words, “You have
heard what I said—That will do.” She suffers when her brothers find
her “insufferably important” or declare her new ideas “crazy.” But
exactly these new ideas about the right and freedom of woman,
which she encounters everywhere, have given a dignity to her own
being which has its influence even without words. On the other hand,
the fact that the fathers lose one legal right after another over the
feminine members of the family has its effect, so that they gradually
change their tone, the clenched fist falls less and less frequently upon
the table, the disdain is silenced, and even in the provinces the family
life is changing more and more from the despotic political
constitution to the democratic, where each one maintains his
position by virtue of his own personality. There are still men it is
true, who wish to confine “woman’s sphere” to the four
“C’s”—“Cooking, clothing, children, church.” But there is no one who
now insists that “a girl cannot learn Mathematics,” or that it is
“unwomanly to pore over books”—sayings which were still often
heard fifty years ago. Certainly there are still men who accept the
cherishing thoughtful care on the part of the women members of the
family as obvious homage. But the men are becoming more and more
numerous who receive these womanly acts of tenderness with waking
joy. Daughters and sisters of earlier times have pardoned the vices of
their fathers and brothers seven and seventy times; those of the
present throw away the fragments of trust and love which have been
irrevocably shattered. The assurance that the daughters and sisters
could do nothing else except pardon, since they were dependent
upon their tormentors, often made the fathers and brothers of earlier
times grossly inconsiderate. The men of to-day will be refined by the
necessity of showing consideration and justice to their daughters and
sisters if they wish to enjoy their presence in the home. Fathers and
brothers have, in a word, gained quite as much spiritually through
the loss of their power to oppress as the daughters and sisters have
gained in being no longer oppressed. And this experience will be
repeated in marriage when man and wife shall be absolutely free and
equal.
CHAPTER V
MOVEMENT UPON MEN AND WOMEN IN
GENERAL
In their struggle for freedom for the same opportunities of study,

for the same fields of work, the same citizenship as man, women
have encountered all possible opposition, from that of the Pope, who
recently pronounced the most positive condemnation of the whole
movement for the emancipation of woman, and that of Parliament,
to the rough pranks of students. Man’s attempt to define the
boundaries of “woman’s natural sphere” continues always. The
woman physician, for example, had to struggle, in her student years,
against prejudice in the dissecting room, and, in her practice, against
the professional jealousy of men. The history of emancipation has
much shameful conduct on the part of man toward woman to record.
Great reluctance to recognise the results of woman’s work is still
common. When this work, in literature and art for instance, is
compared with man’s, the comparison is made not for the purpose of
getting a finer understanding of woman’s peculiar characteristics,
but only to disparage it. The energy which men of the present time
not infrequently lack they cannot endure to recognise in women, who
often possess it in high degree. In the Romance countries, self-
supporting working women are always looked upon as a special caste
—a caste into which a man does not marry however high respect he
pays, theoretically, to “les vierges fortes.”
And yet how different—and more beautiful—are the present
relations between men and women in general, especially among the
Germanic peoples. A friendly comradeship prevails among the young
men and women studying at the university, in art academies, music
schools, business colleges, etc. In the North, this comradeship often
continues from the primary schools, through the grades to the
university, with results advantageous to both sexes. Especially in the
years under twenty, this comradeship has a significance which
cannot be overestimated. Girls, who were, earlier, confined to a
narrow, uninteresting, joyless family circle, now often find in the
circle of masculine and feminine comrades their share of the joy of
youth without which life has no springtime. Youths who formerly
had known no other young women than those with whom they
should never have come in contact, now learn to know soulful, pure-
minded girls, and this gives them a new conception of woman. Both
sexes now experience together the joys of youth in such fresh and
significant forms as folk-dancing, sport, etc. They have opportunity
for stimulating interchange of ideas in a great circle, and quiet
discussion with a few congenial friends. During the last twenty or
thirty years, young men and young women have again begun to
discover one another spiritually, discoveries which since the days of
romanticism have been made only through the stained glass of
literature. In the romantic period, men and women exercised
reciprocally upon one another a humanising influence. A like
influence again obtains at the present time, but upon a much broader
basis. The men and women of romanticism formed a group bound
together only by spiritual relationship, in which the women aspired
to the culture of the men and shared their intellectual interests, while
the men promoted the women’s “desire for men’s culture, art,
knowledge, and distinction” (Geluste nach der Männer Bildung,
Kunst, Weisheit und Ehre.—Schleiermacher). Now, young people
studying in different fields exert a mutual humanising influence and
thereby learn to know one another from the side of intelligence as
well as from that of character and disposition. Thus are dispelled
certain illusions and conceptions almost forced upon them through
which both sexes in the years of adolescence once regarded each
other. Men as well as women obtain a finer criterion for the
conception of “womanliness” and of “manliness”; both discover the
innumerable shadings which these conceptions conceal; both
recognise that the sexes can meet not only upon the erotic plane, but
upon a plane that is universally human; finally, both learn that the
more perfect and complete human beings they become, the more
they have to thank one another for it.
Comprehension in erotic relations is most difficult because, there,
women are far in advance of men. Woman’s ideal of love, however, is
becoming more and more the ideal of young men. Young girls, on
their side, are beginning to understand better the sexual nature of
men. The whole world in which man received his culture, won his
victories, suffered his defeats, is no longer terra incognita to women;
they have lost the blind reverence or the blind hostility with which
they formerly regarded the doings and dealings of men. Men, on the
other hand, are learning that the domestic labours for the comfort of
the family, which they have thus far regarded as the sole duty of
woman, cannot engross her whole soul, that domesticity leaves many
wishes unfulfilled. So both sexes have begun, each on its own side, to
build a bridge across the chasm which law and custom had dug
between them. The young still ponder over the enigmatical
antitheses in their natures, yet they find they have very much that is
human in common with one another. In comradeship, however, that
“chivalry” vanishes, which among other things consisted in the ideal
that the young men had always to bear all the burdens and duties.
Now as a rule, the girl carries her own knapsack on excursions and
pays her share of the expenses. But if she really needs help, the youth
is quite as ready as before to grant it to her, just as she also on her
part is ready to assist according to her strength: honest friendship
has replaced rapturous chivalry. This friendly comradeship often
satisfies the young man’s need of feminine kindness and enjoyment
in those dangerous years when, as a young man said, “Three fourths
of the life of a youth, conscious and unconscious, is sex life.” And
nothing can more effectually prevent him from degrading himself
than access to a circle where in quiet and freedom he meets young
girls, without an indelicate, intruding family surveillance, interfering
and asking him about his “intentions.” If between two such comrades
an erotic feeling finally develops, even if the wooing takes place in a
laboratory instead of a romantic arbour, the possibilities always
exist, in the golden haze of love, of making mistakes. But both have,
however, had opportunities of seeing each other in many character-
illuminating situations; they have observed each other, not only with
their own eyes, but also through the more critical glasses of the
comrade circle. On the other hand, it often happens that discussions
and interchange of letters conjure up a congeniality which exists only
in opinions and temperament, not in nature. It is fortunate when this
is discovered in time. Otherwise bitter conflicts may be the result,
should a strong individual nature wish to mould the other after
himself or after his ideal of man or woman. For that anyone loves the
individuality of another without illusions is still very rarely the case.
It now happens somewhat more frequently, since young people in
comradeship learn to know mutually their ideals and dreams, as well
in erotic as in universally human aspects. But if these ideals and
dreams do give a hint of character, comradeship brings a true
knowledge of character only when it also offers an opportunity of
seeing others act; not only of hearing them speak of themselves.
Such analyses of one’s own soul or the soul of others in the
atmosphere of tea and cigarettes, music and poetry, give the
“interesting” masculine or feminine parasites opportunity to ensnare
a victim, who is then intellectually or erotically, often even
economically, sucked dry.
But even if such an interchange of ideas really enriched all, it can
be carried to excess and become deleterious to energy for work,
directness, and idealism. However beneficial may be the honesty of
to-day in sexual questions, the discussion of the instincts of life
which has now become a commonplace is also dangerous. These
discussions are fraught with the same danger to the roots of human
life as is a continual digging up of the roots of a plant to see how it is
growing.
The earlier a marriage can be consummated, the less is the danger
of freshness being lost in this way; the greater the prospect that man
and wife will grow close together, just as do the man and wife of the
people, through the difficulty of the common struggle for existence.
But if this struggle becomes easier before youth has entirely passed,
then there enters often into the life of the man a crisis which the
practised French call “La maladie de quarante ans”: the need of the
man for a new erotic experience. While those on a lower erotic plane,
to-day as at all times, seek this in transient secret alliances, it leads
those on a higher level in our time to the most tragic of all
separations, where the man—after decades of the most intimate life
together, of the most faithful work together, of mutual
understanding—drives the wife out of the home in order to bring in a
young wife who has never been to him, perhaps never can be to him,
a fellow fighter and helper, as the repudiated wife was, but who has

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Anniversary Logo Design: Richard J. Pacifico

Library of Congress Cataloging-in-Publication Data

QD96.M3 H6413 2007

British Library Cataloguing in Publication Data

1.14 Atmospheric Pressure Secondary Ion Mass Spectrometry 61

3 Detectors and Computers 175

4 Tandem Mass Spectrometry 189

5 Mass Spectrometry/Chromatography Coupling 217

6 Analytical Information 243

6.7 Quantitative Data 260

7 Fragmentation Reactions 273

8 Analysis of Biomolecules 305

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Mass spectrometry’s characteristics have raised it to an outstanding position among analyti-

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m/z Relative m/z Relative

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1 Th = 1 u/e = 1.036 426 × 10−8 kg C−1

1 u = 1 Da = 1.660 540 × 10−27 kg ± 0.59 ppm

Diagram of a Mass Spectrometer

1. Produce ions from the sample in the ionization source.

1940: A.O. NIER isolates uranium-235 [23].

1974: First spectrometers coupled with a high-performance liquid chromatograph by P.J.

Ion Free Path

Table 1 Pressure units. The official SI unit is

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The following comparisons between the life of women, especially

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The relation to the parents, even if the principle of unswerving and

The movement could not however be prevented. And now—how is

In their struggle for freedom for the same opportunities of study,

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