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Chemical
Ionization
Mass
Spectrometry
2nd Edition
Alex G. Harrison
Department of Chemistry
University of Toronto
Toronto, Ontario
Canada
 Library of Congress Cataloging-in-Publication Data

Harrison, Alexander G.
Chemical ionization mass spectrometry / Alex G. Harrison. - - 2nd ed.
p. cm.
Includes bibliographical references and index.
ISBN 0-8493-4254-6
1. Chemical ionization mass spectrometry. I. Title.
QD96.M3H37 1992
54320873—<ic20 91-47678
CIP

This book contains information obtained from authentic and highly regarded sources. Reprinted material
is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable
efforts have been made to publish reliable data and information, but the author and the publisher cannot
assume responsibility for the validity of all materials or for the consequences of their use.
Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic
or mechanical, including photocopying, microfilming, and recording, or by any information storage or
retrieval system, without prior permission in writing from the publisher.
The consent of CRC Press LLC does not extend to copying for general distribution, for promotion, for
creating new works, or for resale. Specific permission must be obtained in writing from CRC Press LLC
for such copying.
Direct all inquiries to CRC Press LLC, 2000 N.W. Corporate Blvd., Boca Raton, Florida 33431.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are
used only for identification and explanation, without intent to infringe.

Visit the CRC Press Web site at www.crcpress.com

© 1992 by CRC Press LLC

No claim to original U.S. Government works

International Standard Book Number 0-8493-4254-6
Library of Congress Card Number 91-47678
 PREFACE

The technique of ionizing a sample of molecules by gas-phase ion/mol-

ecule reactions was first reported in 1966 as an outgrowth of fundamental
studies in gas-phase ion chemistry. In this pioneering paper, Munson and Field
suggested that the method, which they called chemical ionization, might have
useful analytical applications. The past 25 years have proven this prophecy to
be abundantly correct. Chemical ionization provides information which is
complementary to electron ionization and the two methods together are par­
ticularly powerful. In addition, is some cases, chemical ionization provides a
more sensitive method for detecting trace levels of organic compounds. As a
result, chemical ionization is a widely used ionization method in mass spec­
trometry. It also has found extensive applications in structural elucidation
studies and quantitative analytical studies in many branches of chemistry and
biochemistry and in medical and environmental areas. At the same time chemi­
cal ionization studies have provided a large body of information concerning
gas-phase ion chemistry.
The literature of chemical ionizaton mass spectrometry is very large; over
1100 articles have been published using the phrase “chemical ionization” in the
title since the first edition of this monograph was completed in early 1982.
Thus, it appeared appropriate to update the book. The published papers range
from basic studies of the ionization processes to applied analytical problems
where chemical ionization was the method of choice. Clearly, it is impossible
to review all this work. Rather, I have focused on the basic work which forms
the body of knowledge upon which the applied studies are based. Since many
of the scientists beginning work with chemical ionization do not have a
background in gas-phase ion chemistry, I have, once more, provided an exten­
sive review of the basic studies of ion/molecule reaction kinetics and thermo­
dynamics, since these are the foundations upon which chemical ionization is
based. At the same time I have not attempted to include the basic principles of
mass spectrometry; these have received excellent coverage in other books.
My understanding of gas-phase ion chemistry and chemical ionization
mass spectrometry has benefited greatly from the work of many associates over
the past thirty years, and I am indebted to them for their contributions. As usual,
Frank Safian has proven invaluable in the drafting of the diagrams. I am
particularly indebted to my wife, Barbara, who not only has provided the usual
unfailing support but also has entered all the tables into the word processor far
more skillfully than I could have done.

A. G. H.
Toronto, October 1991
 THE AUTHOR

Alex. G. Harrison is Professor of Chemistry at the University of Toronto.

He received his Ph.D. in chemistry from McMaster University in 1956.
After postdoctoral work at McMaster and the National Research Council of
Canada, Ottawa, he joined the staff of the Department of Chemistry, University
of Toronto, as a Lecturer in 1959, becoming Professor of Chemistry in 1967.
He has spent sabbatical leaves in the Department of Molecular Sciences,
University of Warwick (1975), Institut de Chimie Physique, Ecole Polytechnique
Fédérale, Lausanne (1982) and the Department of Chemistry and Biochemis­
try, University of Colorado (1989).
Dr. Harrison is a Fellow of the Chemical Institute of Canada and a member
of the American Chemical Society, the Canadian Society for Mass Spectrom­
etry and the American Society for Mass Spectrometry. He has served on the
Board of Directors of the latter society and as Chairman of the Physical
Chemistry Division and Member of Council of the Chemical Institute of
Canada. From 1988 to 1990 he served as the inaugural President of the
Canadian Society for Mass Spectrometry. He is on the Editorial Advisory
Boards of Organic Mass Spectrometry, Mass Spectrometry Reviews, Interna­
tional Journal o f Mass Spectrometry and Ion Processes and the Journal o f the
American Society for Mass Spectrometry and is an Associate Editor of the
Canadian Journal of Applied Spectroscopy.
Dr. Harrison was an Alfred P. Sloan Fellow 1962-64 and a Killam Re­
search Fellow 1985-87. He has authored or co-authored more than 200 papers
in the area of mass spectrometry and gas-phase ion chemistry. His research
interests lie in the chemistry of gas-phase ions and in the analytical applications
of mass spectrometry.
 TABLE OF CONTENTS

Chapter 1
Introduction ...................................................................................................... 1
I. Preface ................................................................................................. 1
II. Molecular Mass Determination ........................................................... 2
Ill. Structure Elucidation ........................................................................... 3
IV. Identification and Quantitation ........................................................... .4
V. Scope of the Present Work .................................................................. 5
References ........................................................................................................ 5

Chapter 2
Fundamentals of Gas Phase Ion Chemistry .................................................... 7
I. Introduction .......................................................................................... 7
II. Ion/Molecule Collision Rates .............................................................. 8
A. Langevin Ion-Induced Dipole Theory ....................................... 8
B. Average Dipole Orientation (ADO) Theory ........................... 10
Ill. Positive Ion/Molecule Reactions ....................................................... 12
A. Charge Exchange ..................................................................... 12
B. Proton and Hydrogen Atom Transfer ...................................... 15
C. Negative Ion Transfer Reactions ............................................. 18
D. Condensation Reactions ........................................................... 21
E. Clustering or Association Reactions ....................................... 23
IV. Negative Ion/Molecule Reactions ..................................................... 24
A. Electron/Molecule Interactions ................................................ 24
B. Associative Detachment Reactions .......................................... 27
C. Displacement and Elimination Reactions ................................ 28
D. Proton Transfer Reactions ....................................................... 29
E. Charge Exchange Reactions .................................................... 31
F. Association Reactions .............................................................. 31
V. Thermochemical Properties of Gas-Phase Ions ................................ 32
A. Gas Phase Basicities: Proton Affinities (PAs) ....................... 32
B. Hydride Ion Affinities (HIAs) ................................................. 35
C. Electron Affinities (EAs) ......................................................... 36
D. Gas-Phase Acidities: PAs of Anions ...................................... 37
References ...................................................................................................... 41

Chapter 3
Instrumentation for Chemical Ionization ...................................................... 49
I. Introduction ........................................................................................ 49
II. Medium Pressure Mass Spectrometry ............................................... 49
Ill. Atmospheric Pressure Chemical Ionization (APCI) ......................... 53
IV. Fourier Transform Mass Spectrometry (FTMS) ............................... 55
 V. Quadrupole Ion Trap Mass Spectrometer ......................................... 57
VI. Pulsed Positive Ion-Negative Ion Chemical Ionization .................... 59
VII. Sample Introduction in CIMS ........................................................... 60
VIII. Instrumentation for Collision-Induced Dissociation Studies ............ 62
References ...................................................................................................... 65

Chapter 4
Chemical Ionization Reagent Ion Systems ................................................... 71
I. Introduction ........................................................................................ 71
II. Positive Ion Reagent Systems ........................................................... 71
A. Bnmsted Acid Reagent Systems ............................................. 71
B. Hydride Ion Abstraction Reagent Systems ............................. 82
C. Charge Exchange Reagent Systems ........................................ 82
D. Condensation Reaction Reagents ............................................ 85
E. NO as a Positive Ion Reagent System .................................... 86
F. Tetramethylsilane Reagent System .......................................... 88
G. Metal Ion Reagent Systems ..................................................... 89
H. Miscellaneous Positive Ion Reagent Systems ......................... 90
III. Negative Ion Reagent Gas Systems .................................................. 90
A. Electron Capture Reagent Systems ......................................... 90
B. Br0nsted Base Reagent Systems ............................................. 95
C. o- as a Reagent Ion ................................................................ 98
D. 0 2- as a Reagent Ion ............................................................. 100
IV. Sensitivity of Chemical Ionization .................................................. 100
References .................................................................................................... 100

Chapter 5
Chemical Ionization Mass Spectra .............................................................. 113
I. Introduction ...................................................................................... 113
II. A1kanes (C 0 H 2nd ............................................................................ 113
Ill. Alkenes and Cycloalkanes (C 0 H 2 n) ................................................. 115
IV. A1kynes, A1kadienes and Cycloalkenes CCnH 2n_2 ) .......................... 119
V. Aromatic Hydrocarbons .................................................................. 120
VI. Alcohols ........................................................................................... 125
VII. Ethers ............................................................................................... 129
VIII. Aldehydes and Ketones ................................................................... 130
IX. Carboxylic Acids and Esters ........................................................... 131
X. Amines ............................................................................................. 137
XI. Nitro Compounds ............................................................................ 139
XII. Halogenated Compounds ................................................................. 141
XIII. Amino Acids and Derivatives ......................................................... 147
XIV. Carbohydrates and Derivatives ....................................................... 150
References .................................................................................................... 156
Chapter 6
Selected Topics in CIMS ............................................................................ 167
I. Introduction ...................................................................................... 167
II. Isotope Exchange Reactions in Chemical Ionization Studies ........ 167
Ill. Stereochemical Effects in CIMS ..................................................... 172
IV. Tandem Mass Spectrometry and Chemical Ionization ................... 185
V. Reactive Collisions in Quadrupole Collision Cells ........................ 194
References .................................................................................................... 195
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 Chapter 1

INTRODUCTION

I. PREFACE

The technique of chemical ionization (Cl), first introduced by Munson and

Field^ in 1966, is a direct outgrowth of fundamental studies of ion/molecule
interactions; as such the technique is based on the knowledge developed from
these fundamental studies and makes use of the instrumentation developed for
such studies. Since its initial introduction, chemical ionization mass spectrom­
etry (CIMS) has developed into a powerful and versatile tool for the identification
and quantitation of organic molecules and, consequently, has found extensive
application in many branches of chemistry and biochemistry and in medical
and environmental fields.
In CIMS, ionization of the sample of interest is effected by gas phase ion/
molecule reactions rather than by electron impact, photon impact, or field
ionization/desorption; frequently CIMS provides information which is comple­
mentary to these techniques rather than supplementary. Particularly in structure
elucidation, it is common to determine both the electron ionization (El) and Cl
mass spectra. Although much of the earlier work in CIMS utilized positive ion/
molecule reactions, there has been, over the past 15 years, an increased interest
in negative ion/molecule reactions as an ionization method. This later devel­
opment of negative ion CIMS occurred, in part, because El studies at low
source pressures showed, in general, a low sensitivity for negative ion production
as well as a strong dependence of negative ion mass spectra on the ionizing
electron energy. In addition, many commercial mass spectrometers were not
equipped to operate in the negative ion mode. This latter problem has been
rectified and most commercial mass spectrometers now operate readily in the
negative ion mode which, under Cl conditions, often shows ion signals at least
as strong as those observed in the positive ion mode.
The essential reactions in Cl are given in general form in Reactions 1 to
3. Ionization of the reagent gas (present in large excess), frequently by electron
impact, usually is followed by ion/molecule reactions involving the primary
ions and the reagent gas neutrals and produces the Cl reagent ion or reagent ion
array (Reaction 1). This reagent ion or reagent ion array represents the stable

e+R R-
(1)

R “ 4-A - > Ar +N, (2)

 Chemical Ionization Mass Spectometry

->A^+N,

A; ■N.
(3)
A- +N.

end product(s) of the ion/molecule reactions involving the reagent gas. Colli­
sion of the reagent ion(s), R-, with the additive (present at low concentrations,
usually <1% of the reagent gas) produces an ion, A~ characteristic of the
additive (Reaction 2). This additive ion may fragment by one or more path­
ways, as in Reaction 3, or, infrequently, react with the reagent gas; the final
array of ions A~ to At when mass analyzed in the usual manner, provides the
Cl mass spectrum of the additive gas A as effected by the reagent gas R.
A large part of the usefulness of CIMS rests with the fact that a large
variety of reagent gases and, hence, reagent ions can be employed to effect
ionization. To a considerable extent, the choice of reagent systems can be
tailored to the problem to be solved. The problems amenable to solution by the
Cl technique can be divided into three rough categories: (1) molecular mass
determination, (2) structure elucidation, and (3) identification and quantitation.

IL MOLECULAR MASS DETERMINATION

When a gaseous sample of a polyatomic species is bombarded with

electrons at sample pressures of torr, the initial electron/molecule inter­
action produces an assembly of molecular ions with internal energies ranging
from 0 to about 10 eV. The energized molecular ions fragment to form the
fragment ions observed in the El mass spectrum.“ For some classes of com­
pounds, the critical energy required for fragmentation of the molecular ion is
extremely low (or zero) with the result that no molecular ions are seen in the
mass spectrum; in effect, fragmentation is so facile that no molecular ions
survive for the ~10~^ s that elapses before mass analysis occurs. When this
happens, the molecular mass can be established only with considerable diffi­
culty by El methods. The aim of Cl in these instances is to produce, by suitable
choice of reagent ions, abundant ions characteristic of the sample and provid­
ing the molecular mass of the sample molecules.
In positive ion Cl the most commonly used ionization reaction for such
purposes has been proton transfer (Reaction 4) from the reagent ion(s), BH'^,
to the sample molecule M, where AH^ is given by the proton affinity (PA) of

+M MH^ + B, AH, (4)

B less the PA of M. The extent of fragmentation of MH^ depends on its internal

energy which, in turn, depends on AH^, the exothermicity of the proton transfer
reaction. The magnitude of AH^ and thus, the extent of fragmentation of
 Introduction 3

usually can be controlled by suitable choice of reagent gas; in addition, the

stability of the even-electron MH^ ion may be considerably greater than the
stability of the odd-electron species formed in the El process.
An analogous proton transfer (Reaction 5) can be utilized in negative ion
Cl; AH3 is equal to PA([M - H]~) - PA(X")

X~ -F M -^ [M -H r -hHX (5)

or, alternatively, is given by the gas phase acidity of M less the gas phase
acidity of XH. Again, by suitable choice of reagent ion, the exothermicity of
the proton transfer reaction can be made sufficiently small as to preclude
extensive fragmentation of [M - H]“. In addition, the exothermicity of the
reaction appears to reside primarily in the bond formed between X and H and,
therefore, is unavailable to promote fragmentation of [M - H]”.
A number of other reactions also have been used to provide molecular
mass information. These include hydride abstraction (Reaction 6), electron
attachment (Reaction 7), electron transfer (Reaction 8), and adduct or cluster
ion formation (Reaction 9). It should be noted that formation of cluster ions

X""-F M [M - H f + XH ( 6)

e+M ^ M (7)

X"^ + M M - + X (8)

X-+M-^M'X- (9)

usually requires third-body stabilization and the rates of such reactions may be
considerably slower than the rates of bimolecular processes such as Reactions
4 to 8.
In the literature, ions characteristic of the molecular mass have been called
quasimolecular ions independent of their exact identity as MH^, [M - H]- or
M X-. This sloppy terminology, which has been criticized recently,^ should be
discontinued; the ions from which the molecular mass is established should be
clearly identified and not hidden under a generic name.

III. STRUCTURE ELUCIDATION

When a sample of unknown chemical structure is being examined, one

usually desires structural information as well as molecular mass information
from the Cl mass spectrum. Ideally, one would like to have an array of reagent
ions which give characteristic reactions with each possible functional group.
4 Chemical Ionization Mass Spectometry

thus signalling the presence or absence of a particular group. Except for a very
few cases, this ideal has not been attained and, consequently, other approaches
must be used.
The majority of structural studies have used positive ion proton transfer Cl
methods. The major fragmentation reactions of the even-electron MH^ ions
formed in Reaction 4 involve elimination of stable neutral molecules, HY,
where Y is a functional group such as OR, NR2, halogen, etc., present in the
molecule. This fragmentation mode frequently is quite different from the
fragmentation modes of the odd-electron molecular ion formed by El, and the
structural information obtained by the two techniques often is complementary.
In those cases where the fragment ions formed by El are structurally
informative but no molecular mass information is provided by the El mass
spectrum, mixed proton transfer/charge exchange reagent systems can be used.
The proton transfer reagent forms MH^ ions indicative of molecular mass,
while the charge exchange reagent, by dissociative charge exchange, gives the
same fragment ions as are produced in El since the initial ion/molecule
interaction produces the odd-electron molecular ion.
The methodology of structure elucidation by negative ion Cl is less
developed, although general rules for the fragmentation of negative ions are
being developed."^ Increasingly, structural information is being derived by
collision-induced dissociation, in a tandem mass spectrometer, of the MH^ or
[M - H]“ ions formed in a gentle Cl reaction.

IV. IDENTIFICATION AND QUANTITATION

This application of mass spectrometry is undoubtedly the most common,

whether employing El or CL The aim is to identify a known substance and to
measure quantitatively the amount of this substance present in a frequently
complex matrix. Although, in principle, it should be possible to selectively
ionize the component of interest in the matrix by a suitable Cl reaction, this
approach has seen relatively little use. In the majority of studies, separation of
the mixture in time is achieved by application of a chromatographic technique
with direct introduction of the chromatographic effluent into the mass spec­
trometer ion source. The ionization reaction requires only that a relatively
small number of ions characteristic of the component be produced in high yield
to achieve maximum sensitivity of detection. In general, formation of two or
more ions is preferred, since identification is made more certain by the require­
ments that the appropriate ion signals must show the same intensity/time
profile as well as the appropriate relative intensities. Cairns et al.^ recently have
discussed in detail the criteria for confirmation of the presence of a component
in a complex matrix.
An alternative to separation of the components in time is separation of the
components by mass in so-called MS/MS experiments.^’^ In this approach the
complex mixture is ionized, usually by gentle methods, to produce character­
 Introduction 5

istic ions such as MH^ or [M - H]~ from each component. Mass selection of
the ion suspected to arise from the component of interest and collision-induced
dissociation of this ion in a tandem mass spectrometer leads to a fragment ion
or ions which are characteristic of the component. In practice, it has been found
that some separation by chromatographic methods usually is advantageous
when this approach to identification is used.
The problems of quantitation, particularly in gas chromatography work,
have been discussed in detail^ and will not be repeated here. Because of poten­
tial losses of the analyte during the workup of the sample, an internal standard
of some type is added to the mixture at the earliest possible stage of sample
handling. This internal standard should have chemical and physical properties
similar to the component of interest so that the losses of the two will be the
same. Knowing the amount of standard added, the amount of unknown present
can be deduced from a comparison of the mass spectral response to the
unknown and the standard.

V. SCOPE OF THE PRESENT W ORK

These introductory comments serve to indicate the scope of the present

monograph. CIMS rests firmly on the foundations established from fundamen­
tal studies of gas-phase ion chemistry. These foundations are discussed in
Chapter 2. The techniques of mass spectrometry peculiar to Cl studies are
discussed in Chapter 3, although no attempt is made to review the basic
principles of mass spectrometry; for these the reader is referred to other
s o u r c e s . A particularly elegant comparison of various mass analyzers has
appeared recently. The reagent gases used in CIMS have been many, with
various areas of utility; the more important are discussed in Chapter 4. Similarly,
the range of compounds studied by chemical ionization mass spectrometry is
vast. Those for which systematic studies have been made, allowing generali­
zations to be drawn, are discussed in Chapter 5. Finally, a number of more
specialized topics are discussed in Chapter 6.

REFERENCES

1. Munson, M.S.B. and Field, F.H., Chemical ionization mass spectrometry. I. General
introduction, J. Am. Chem. Soc., 88, 2621, 1966.
2. Harrison, A.G. and Tsang, C.W., The origin of mass spectra, in Biochemical Applications
of Mass Spectrometry, Waller, G.R., Ed., John Wiley & Sons, New York, 1972.
3. Bursey, M.M., Comment to readers. Style and the lack of it. Mass Spectrom. Rev., 10, 1,
1991.
4. Bowie, J.H., The fragmentation of even-electron organic ions. Mass Spectrom. Rev., 9, 349,
1990.
 Chemical Ionization Mass Spectometry

5. McLafferty, F.W., Ed., Tandem Mass Spectrometry, John Wiley & Sons, New York, 1983.
6. Busch, K.L., Glish, G.L. and McLuckey, S.A., Mass Spectrometry!Mass Spectrometry;
Techniques and Applications of Tandem Mass Spectrometry, VCH Publishers, New York,
1988.
7. Cairns, T., Siegmund, E.G., and Stamp, J.J., Evolving criteria for the confirmation of trace
level residues in food and drugs by mass spectrometry. Part I, Mass Spectrom. Rev., 8, 93,
1989. Part II, Mass Spectrom. Rev., 8, 127, 1989.
8. Millard, B.J., Quantitative Mass Spectrometry, Heyden and Son, London, 1978.
9. Roboz, J., Introduction to Mass Spectrometry, Interscience, New York, 1968.
10. Watson, J.T., Introduction to Mass Spectrometry, 2nd. Edition, Raven Press, New York,
1985.
11. Chapman, J.R., Practical Organic Mass Spectrometry, John Wiley & Sons, Chichester,
1985.
12. White, F.A. and Wood, G.M., Mass Spectrometry; Applications to Science and Engineer­
ing, John Wiley & Sons, New York, 1986.
13. Brunnee, C., The ideal mass analyzer: fact or fiction, Int. J. Mass Spectrom. Ion Processes,
16, 125, 1987.
 Chapter 2
FUNDAMENTALS OF GAS-PHASE ION CHEMISTRY

L INTRODUCTION

From the earliest days of mass spectrometry, ions were observed which
generally were agreed to have arisen from reactions between ions and neutral
molecules. An ion of m/z 3 was observed by Dempster^ in 1916 and identified
as ; its formation by Reaction 1 was well established by 1925.^^^ In 1928,

a : + H2 - > H 3 + H ( 1)

Hogness and Harkness^ reported the formation of and 13" in iodine vapor
subjected to electron impact. lon/molecule reactions were observed in several
other systems during the 1920s; the early work has been reviewed by Smyth^
and by Thompson.^ With improvements in instrumentation and techniques,
particularly vacuum technology, the nuisance of secondary processes was
largely eliminated, and studies of ion/molecule reactions largely ceased. The
main interests in mass spectrometry during the period 1930 to 1950 lay in the
physics of ionization and dissociation, in the determination of isotopic masses
and abundances, and in the development of analytical mass spectrometry using
primarily electron ionization.
The modem era of ion/molecule reaction studies began in the early 1950s
when the ion CH^, formed by the reaction

C H t‘ + C H , ‘ CH^ + CH3 ( 2)

was discovered by TaTroze and Lyubimova^ in the Soviet Union and, indepen­
dently soon thereafter, by Stevenson and Schissler^ and Field, Franklin, and
Lampe^ in the U.S. The observation of CH^ as a stable species aroused the
interest of chemists concerned with structure and bonding, while the observa­
tion that Reaction 2 was considerably faster than reactions involving only
neutral species suggested that ion/molecule reactions might play an important
role in radiation chemistry and aroused the interest of radiation chemists. In
addition, much improved equipment was available for the controlled study of
ionic collision processes. As a result a number of studies of gas-phase ion/
molecule reactions were undertaken. Since that beginning, the study of the
products, distribution, rates, and equilibria of gas-phase ionic reactions has
become a major field of scientific activity with applications in many diverse
fields. In the course of these studies, many advances in instmmentation have
been made. The advances in instrumentation and in the understanding of gas-
phase ion chemistry have been reviewed in numerous articles^^^^ and books.
The instrumentation developed for the study of ion/molecule reactions has
led to the instrumentation for CIMS; this aspect is discussed in Chapter 3. The
large body of kinetic and thermochemical data derived from the fundamental
 Chemical Ionization Mass Spectometry

FIGURE 1. Schematic ion/molecule collision.

studies constitutes the foundation upon which the chemistry of the chemical
ionization technique is based; this body of data is reviewed in the remainder of
this chapter.

II. ION/M OLECULE COLLISION RATES

The usefulness of an ion/molecule reaction in a chemical ionization sys­

tem depends, in part, on the identity of the reaction products and, in part, on
the rate of the reaction. The latter is important since only those reactions which
are rapid can be expected to show adequate product yields. The upper limit to
the reaction rate is given by the collision rate. The present section reviews the
estimation from theory of collision rates of ions with nonpolar and with polar
molecules.

A. Langevin Ion-Induced Dipole Theory

When an ion interacts with a nonpolar molecule it induces a dipole in the
neutral; at moderately long range the only interaction of importance is the
resultant ion-induced dipole interaction. Eyring et al.^*^ first calculated in 1936
the classical capture collision cross section for the reaction using
absolute rate theory and a model of a structureless point charge interacting with
a point-polarizable molecule. A general form of the capture collision cross
section was derived by Vogt and Wannier,^^ and elaborated by Gioumousis and
Stevenson^^ based on a model first developed by Langevin.^"' The theoretical
development has been discussed extensively by a number of authors; the
present summary is based largely on the treatment of Su and Bowers.^^
The theory calculates the collision cross section for an ion/molecule pair
with a given relative velocity where both partners are assumed to be point
particles with no internal energy and the interaction between the two is as­
sumed to arise from ion-induced dipole forces only. Thus, for an ion and a
molecule approaching each other with a relative velocity v and impact param­
eter b (Figure 1) the classical potential at an ion/molecule separation r is given by

V(r) = - a q - / 2 r ‘* (3)

where a is the polarizability of the neutral and q is the charge on the ion. For
r < oo, the relative energy of the system, E^, is the sum of the instantaneous
kinetic energy and the potential energy:
 Fundamentals of Gas-Phase Ion Chemistry

FIGURE 2. V vs. r for critical impact pa-

rameter b .

E ^ = 4 ^ v ^ = E ^ _ J r ) + V(r) (4)

where \i is the reduced mass. There are two components to Ej^-^(r), the trans­
lational energy along the line of center of the collision, E^j.^^g(r), and the energy
of relative rotation of the particles, Ej.^^(r), where the latter is given by

E^„,(r) = L 7 2 ^ i F = ^ v V / 2F (5)

where L is the classical orbital angular momentum of the two particles. The
rotational energy is associated with a outwardly acting centrifugal force and the
effective potential of the ion/molecule system can be represented as the sum of
the central potential energy and this centrifugal potential energy

U ff (*■) = - ( a q V 2 r h + ( L - /2 R r h ( 6)

The total relative energy of the system, thus, is

E r = E trans ( r ^)-bV,effTr)
^^ (7)

The variation of Vg^^(r) with r at constant E^ depends on the value of the

impact parameter b. For b = 0, there is no contribution from the centrifugal
potential and Vg^^(r) is attractive for all values of r. When b > 0 the centrifugal
potential creates a so-called “centrifugal barrier” to a capture collision. The
special case (b = b^) where the centrifugal barrier height equals E^. is shown in
Figure 2; at r^, Vg^j^(r) = E^. and thus, from Equation 7 E^j.^^g(r) = 0 and the
particles will orbit the scattering center with a constant ion/molecule separation
r^. For all impact parameters less than b^, a capture collision will occur, where
a capture collision is defined as one in which the particles have appropriate
energy and appropriate impact parameters to pass through r = 0. (For real ions
and molecules there would, of course, be some finite minimum value of r > 0).
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10 Chemical Ionization Mass Spectometry

For impact parameters greater than the centrifugal barrier prevents capture
and the particles are simply scattered at large values of r.
The capture collision cross section at a given velocity v is defined by

cr(v) = 7T:b; (8)

Thus, the critical impact parameter b^ is the impact parameter such that
Vg^^(r) = Ej. and can be evaluated from the conditions that 5Vg^^(r)/dr = 0 and
V^ff(r) = at r r^, i.e.,

dVeff/3r = 0 = ( i J / pr-" j + ¡ 2 a q ^ / r (9)

=E ( 10)

These restrictions lead to

=(2q/bc^)(«/li) ( 11)

b^ = (4 a q V )iv -''‘’ ( 12)

which leads to the distance of closest approach = b^,/2'^- and to a capture

collision cross section and collision rate constant given by

c^(v) = Ttb; = (2ttq/v)(a/p)2 (13)

k, = v a ^ ( v ) = 27tq(a/p)2 (14)

Hence, if only ion-induced dipole interactions are involved, classical

collision theory predicts that the capture cross section should vary inversely as
the relative velocity of the colliding pair, while the capture rate constant,
frequently called the Langevin rate constant, should be independent of the
relative velocity and the temperature. As will be seen in the following. Equa­
tion 14 predicts reasonably well the maximum rate constants for ion/molecule
reactions involving nonpolar molecules. This indicates that reaction occurs on
every collision for many ion/molecule pairs; consequently, there can be no
activation energy for the reaction. The rate constant predicted from Equation
14 is of the order of 1 x 10“^ cm^ molecule“^ s“^ or about 6 x 10^ ^ L mol“^s“^

B. Average Dipole Orientation (ADO) Theory

Although Equation 14 predicts reasonably well the maximum rate con­
stants for reactions involving nonpolar molecules, it seriously underestimates
the rate constants of most ion/molecule reactions involving polar molecules.
For these cases, it was shown first by Moran and HamilP^ that ion dipole forces
could not be ignored. Where such forces are important, the effective potential,
analogous to Equation 6, becomes
 Fundamentals of Gas-Phase Ion Chemistry 11

where ¡Lij^ is the dipole moment and 0 is the angle the dipole makes with the
center of collision. Hamill and colleagues^^’^^ made the simplifying assump­
tion that the dipole ‘docks in” on the ion (0 = 0) and derived, by the approach
outlined above, the capture collision rate constant:

kLD('') = l 2 n q /(l- a~ -r (16)

where the subscript LD refers to the locked-in dipole approximation. In this

case, the rate constant depends on the relative velocity of the colliding pair and
gives*^^ for a Maxwell-Boltzmann distribution of relative velocities:

k (thermal) = 27iq/ a- 2/TikgT (17)

where kg is Boltzmann’s constant and T is the absolute temperature.

It has been shown"^^^ that Equations 16 and 17 seriously overestimate the
ion-dipole effect on ion/molecule reaction rate constants; presumably locking-
in of the dipole does not occur. Thus, a more reasonable expression for the
thermal energy rate constant is

kADo(*^™) = [ a - +C|j.j^(2/jtkj T - (18)

where C, the dipole locking constant, reflects the extent to which the dipole of
the molecule orients itself with the incoming charge and may have values from
0 (no alignment) to 1 (locking-in). Bowers and colleagues have developed the
average dipole orientation (ADO) theory of ion/polar molecule collisions in
which they calculate by classical statistical theory either the average orienta­
tion angle 0^2 43 average cos 0 (i.e., the average effective potential of the
ion/polar molecule system).“^^ The two approaches give similar results. From
the results of such calculations, they deduced that the dipole locking constant
C of Equation 18 can be parameterized. It turns out that, at constant tempera­
ture, C is a function of only. Values of C as a function of
covering a temperature range of 150 to 500 K, have been presented;"^^ typical
plots are shown in Figure 3. For large values of Pg/a^^^, C reaches a limiting
value of -0.26. Thus, the effect of ion dipole interactions is much less than
predicted from the simple model involving locking-in of the dipole (C = 1),
although enhancement of the rate constant by a factor of 2 to 4 over the ion-
induced dipole value is possible for reactions where the molecule has a large
dipole moment.
A number of studies,‘^“ '^^’'^^’'^^ principally involving simple proton transfer
reactions have shown that the ADO theory in the form of Equation 18, with the
12 Chemical Ionization Mass Spectometry

FIGURE 3. Dipole locking constant C as a function of and tempera­

ture. Data from Su and Bowers

value of C derived from adequately predicts the maximum rate con­

stants for ion/polar molecule reactions. These will be discussed in more detail
in the following sections. The ADO theory also predicts a much smaller
dependence of rate constant on temperature than does the locked dipole expres­
sion, Equation 17; this also has been confirmed e x p e r i m e n t a l l y F u r t h e r
extensions of the theory to include conservation of angular momentum (AADO
t h e o r y a n d to include ion-quadrupole interactions (AQO theory)^ ^have been
reported. These normally are relatively small effects and the reader is referred
to the original publications or to the review by Su and Bowers^^ for details.

III. POSITIVE lO N /M OLECULE REACTIONS

A wide variety of ion/molecule reactions involving positive ions have

been studied. The present review will concentrate primarily on the type of
product ions formed and on the reaction rates. The classification system used,
while essentially arbitrary, is based largely on the identity of the product ions
formed. The rate constants listed in this review are illustrative of the results
available; a complete tabulation of kinetic data to 1986 is available.

A. Charge Exchange
The interaction of a positive ion with a neutral molecule may lead to
charge exchange, Reaction 19; the reaction will be exothermic if the
 Fundamentals of Gas-Phase Ion Chemistry 13

TABLE 1
Recombination Energies of Gaseous lons^

RE
Ion (eV f

21.6
T^1/2 21.7
Ar^-^P3/2 15.8
^P,/2 15.9
Nf 15.3
14.0
^1/2 14.7
CO^ 14.0
coy 13.8
Xe^'2p3/, 12.1
^^1/2 13.4
COS+ 11.2
CS+- ~9.5 or 10.0
NO^ 8.5 or 9.5
9.3

^ From Lindholm.^^’^"^

AH = IE( M) - RE( X (19)

recombination energy (RE) of the reactant ion is greater than the ionization
energy (IE) of the neutral M. The RE of X"^ is defined as the exothermicity of
the gas phase reaction

X^ + e ^ X -A H = RE( x ^ ) (20 )

Eor monatomic ions, the RE has the same numerical value as the ionization
of the neutral; this is not necessarily so for diatomic and polyatomic species
since the product neutral in these cases may have excess vibrational/rotational
energy or, in some cases, may be formed in an excited electronic state. A
selection of RE, taken from the summaries by Lindholm,^^’^"^ is presented in
Table 1. Eor polyatomic M, the exothermicity of the charge exchange reaction
appears to remain largely as internal energy of the M^' product. '’-^If this internal
energy is sufficiently large the ion may undergo fragmentation; the frag­
mentation reactions observed will be the same as those observed following
electron ionization since, in both cases, fragmentation commences from the
odd-electron molecular ion. The important difference is that the molecular ions
formed by electron ionization will have a distribution or range of internal
energies while those formed by charge exchange will have an internal energy
determined by the exothermicity of Reaction 19. Since the relative importance
of the different fragmentation channels is dependent on the internal energy, the
product distribution from charge exchange reactions will depend on the exo­
thermicity of the reaction (see Section II.C, Chapter 4).
14 Chemical Ionization Mass Spectometry

TABLE 2
Rate Constants for Charge Exchange Between Rare Gas Ions and
Nonpolar Molecules

react coll
Reactants (cm^ molecule“^ x 10^) (cm^ molecule"^ S"^ x 10^)

Ne+ + CH4 0.07^ 1.26

Kr+ + CH, 1.26" 1.03
1.03^^
1. 20"
Ar^ + CH, 1.34" 1.12
0.98^
1. 10"
Ne^-+ C.Hg 0.98" 1.40
Ar^' + 1.07" 1.16
Kr+ + C~H^ 0.75" 1.03
Xe^ + c“h ^ 0.84" 0.98
Ne+- + C^Hg 1. 21 " 1.55
Ar"-- + C'h . 1. 20 " 1.25

" From Bowers and Elleman.^^

^ From Ausloos et al.^^
" From Li and Harrison.^^

Charge exchange reactions of polyatomic molecules have been studied

extensively using tandem mass s pe c t r ome t e r s . Howe ve r , such studies have
involved reactant ions with >3 eV kinetic energy and have been more con­
cerned with product distributions than with the measurement of reaction rate
constants. More recently, charge exchange reactions at nearer thermal energies
have been studied using chemical ionization techniques,^^ but again the interest
has been in product ion distributions rather than reaction rates. Consequently,
the information concerning the rate constants of charge exchange reactions at
low kinetic energies is rather limited. Table 2 summarizes rate constants
measured for charge exchange involving rare gas ions and some simple al­
kanes. The table also compares the measured reaction rate constants with
collision rate constants calculated by Equation 14. For no case does the
measured rate constant exceed the collision rate constant. With the exception
of the reaction Ne^' + CH4 the efficiencies of the reactions are quite high.
Table 3 records rate constants measured for charge exchange between the
ions Ne^, Ar^', N^, Kr"^' and CO^ and the polar molecules dimethyl ether
= 1.30D), methyl alcohol (pj) = 1.7ID), and acetone (Pj^ = 2.88D). Also in­
cluded in the table are the collision rate constants calculated from the ADO
theory. Equation 18. The latter have been separated into the ion-induced dipole
and ion-permanent dipole contributions to illustrate the magnitude of each. The
ion-permanent dipole contribution varies with the dipole moment of the neu­
tral, and for the most polar molecule, acetone, is equal in magnitude to the ion-
induced dipole contribution. Again, within experimental error, the measured
reaction rate constants do not exceed the collision rate constants, although in
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 Many of the Scribes were of the sect of the Pharisees. Thus
St. Paul himself, who was educated for a Scribe, first at the
university of Tarsus, and after that in Jerusalem, at the feet of
Gamaliel (one of the most learned Scribes or doctors of the law that
were then in the nation) declares of himself before the council, 93I
am a Pharisee the son of a Pharisee: and before king Agrippa,
94After the straitest sect of our religion I lived a Pharisee. And the
whole body of the Scribes generally esteemed and acted in concert
with the Pharisees. Hence we find our Saviour so frequently coupling
them together, as coming in many respects under the same
consideration. In this place they seem to be mentioned together, as
the most eminent professors of religion: the former of whom were
accounted the wisest, the latter the holiest of men.

3. What the righteousness of the Scribes and Pharisees really

was, it is not difficult to determine. Our Lord has preserved an
authentic account, which one of them gave of himself. And he is
clear and full in describing his own righteousness; and cannot be
supposed to have omitted any part of it. He went up indeed into the
temple to pray: but was so intent upon his own virtues, that he
forgot the design upon which he came. For ’tis remarkable, he does
not properly pray at all. He only tells God, how wise and good he
was. God, I thank thee, that I am not as other men are;
extortioners, unjust, adulterers; or even as this Publican. I fast twice
in the week; I give tithes of all that I possess. His righteousness
therefore consisted of three parts, first, saith he, I am not as other
men are. I am not an extortioner, not unjust, not an adulterer; not
even as this Publican. Secondly, I fast twice in the week; and thirdly,
give tithes of all that I possess.

I am not as other men are. This is not a small point. It is not

every man that can say this. It is as if he had said, I do not suffer
myself to be carried away by that great torrent, custom. I live not by
custom, but by reason; not by the examples of men, but by the
word of God. I am not an extortioner, not unjust, not an adulterer:
however common these sins are even among those who are called
the people of God: (extortion, in particular, a kind of legal injustice:
not punishable by any human law, the making gain of another’s
ignorance or necessity, having filled every corner of the land) nor
even as this Publican; not guilty of any open or presumptuous sin:
not an outward sinner: but a fair, honest man, of blameless life and
conversation.

4. I fast twice in the week. There is more implied in this, than we

may at first be sensible of. All the stricter Pharisees observed the
weekly fasts; namely, every Monday and Thursday. On the former
day, they fasted in memory of Moses receiving on that day (as their
tradition taught) the two tables of stone written by the finger of
God: on the latter, in memory of his casting them out of his hand,
when he saw the people dancing round the golden calf. On these
days, they took no sustenance at all till three in the afternoon; the
hour at which they began to offer up the evening sacrifice in the
temple. Till that hour it was their custom to remain in the temple, in
some of the corners, apartments or courts thereof; that they might
be ready to assist at all the sacrifices, and to join in all the public
prayers. The time between, they were accustomed to employ, partly
in private addresses to God, partly in searching the scriptures, in
reading the law and the prophets, and in meditating thereon. Thus
much is implied in, I fast twice in the week, the second branch of
the righteousness of a Pharisee.

5. I give tithes of all that I possess. This the Pharisees did with
the utmost exactness. They would not except the most
inconsiderable thing, no, not mint, anise and cummin. They would
not keep back the least part of what they believed properly to
belong to God; but gave a full tenth of their whole substance yearly,
and of all their increase, whatsoever it was.

Yea, the stricter Pharisees (as has been often observed, by those
who are versed in the ancient Jewish writings) not content with
giving one tenth of their substance to God, in his priests and Levites,
gave another tenth to God in the poor, and that continually. They
gave the same proportion of all they had in alms, as they were
accustomed to give in tithes. And this likewise they adjusted with
the utmost exactness, that they might not keep back any part, but
might fully render unto God the things which were God’s, as they
accounted this to be. So that, upon the whole, they gave away, from
year to year, an entire fifth of all that they possest.

6. This was the righteousness of the Scribes and Pharisees: a

righteousness, which in many respects, went far beyond the
conception which many have been accustomed to entertain
concerning it. But perhaps, it will be said, it was all false and
feigned; for they were all a company of hypocrites.—Some of them
doubtless were; men who had really no religion at all; no fear of
God, or desire to please him: who had no concern for the honour
that cometh of God, but only for the praise of men. And these are
they whom our Lord so severely condemns, so sharply reproves on
many occasions. But we must not suppose, because many Pharisees
were hypocrites, therefore all were so. Nor indeed is hypocrisy by
any means essential to the character of a Pharisee. This is not the
distinguishing mark of their sect. It is rather this, (according to our
Lord’s account) They trusted in themselves that they were righteous,
and despised others. This is their genuine badge. But the Pharisee of
this kind cannot be a hypocrite. He must be, in the common sense,
sincere: otherwise he could not trust in himself that he is righteous.
The man who was here commending himself to God, unquestionably
thought himself righteous. Consequently, he was no hypocrite: he
was not conscious to himself of any insincerity. He now spoke to God
just what he thought, namely, that he was abundantly better than
other men.

But the example of St. Paul, were there no other, is sufficient, to

put this out of all question. He could not only say, when he was a
Christian, 95Herein do I exercise myself to have always a conscience
void of offence, toward God and toward men: but even concerning
the time when he was a Pharisee; 96Men and brethren, I have lived
in all good conscience before God until this day. He was therefore
sincere when he was a Pharisee, as well as when he was a Christian.
He was no more an hypocrite when he persecuted the church, than
when he preached the faith which once he persecuted. Let this then
be added to the righteousness of the Scribes and Pharisees, a
sincere belief that they are righteous, and in all things doing God
service.

7. And yet, Except your righteousness, saith our Lord, shall

exceed the righteousness of the Scribes and Pharisees, ye shall in no
case enter into the kingdom of heaven. A solemn and weighty
declaration! And which it behoves all who are called by the name of
Christ, seriously and deeply to consider. But before we enquire, how
our righteousness may exceed theirs, let us examine, whether at
present we come up to it?

*First, a Pharisee was not as other men are. In externals he was

singularly good. Are we so? Do we dare to be singular at all? Do we
not rather swim with the stream? Do we not many times dispense
with religion and reason together, because we would not look
particular? Are we not often more afraid of being out of the fashion,
than being out of the way of salvation? Have we courage to stem
the tide? To run counter to the world? To obey God rather than
man? Otherwise the Pharisee leaves us behind at the very first step.
’Tis well if we overtake him any more.

But to come closer. Can we use his first plea with God, which is in
substance, “I do no harm. I live in no outward sin; I do nothing, for
which my own heart condemns me.” Do you not? Are you sure of
that? Do you live in no practice, for which your own heart condemns
you? If you are not an adulterer, if you are not unchaste, either in
word or deed, are you not unjust? The grand measure of justice, as
well as of mercy, is, Do unto others as thou wouldest they should do
unto thee. Do you walk by this rule? Do you never do unto any what
you would not they should do unto you? Nay, are you not grossly
unjust? Are you not an extortioner? Do you not make a gain of any
one’s ignorance or necessity? Neither in buying nor selling? Suppose
you were engaged in trade, do you demand, do you receive no more
than the real value of what you sell? Do you demand, do you receive
no more of the ignorant than of the knowing; of a little child, than of
an experienced trader? If you do, why does not your heart condemn
you? You are a barefaced extortioner. Do you demand no more than
the usual price of goods, of any who is in pressing want? Who must
have, and that without delay, the things which you can only furnish
him with? If you do, this also is flat extortion. Indeed you do not
come up to the righteousness of a Pharisee.

8. A Pharisee, secondly, (to express his sense in our common

way) used all the means of grace. As he fasted often and much,
twice in every week, so he attended all the sacrifices. He was
constant in public and private prayer, and in reading and hearing the
scriptures. Do you go as far as this? Do you fast much and often?
Twice in the week? I fear not. Once, at least; “on all Fridays in the
year?” (So our church clearly and peremptorily enjoins all her
members to do: to observe all these, as well as the vigils and the
forty days of lent, as “days of fasting or abstinence.”) Do you fast
twice in the year? I am afraid, some among us cannot plead even
this!—Do you neglect no opportunity of attending and partaking of
the Christian Sacrifice? How many are they, who call themselves
Christians, and yet are utterly regardless of it? Yet do not eat of that
bread, or drink of that cup, for months, perhaps years, together? Do
you every day, either hear the scriptures, or read them and meditate
thereon? Do you join in prayer with the great congregation? Daily, if
you have opportunity: if not whenever you can, particularly on that
day, which you remember, to keep it holy? Do you strive to make
opportunities? Are you glad when they say unto you, we will go into
the house of the Lord? Are you zealous of, and diligent in private
prayer? Do you suffer no day to pass without it? Rather, are not
some of you so far, from spending therein (with the Pharisee)
several hours in one day, that you think one hour full enough, if not
too much? Do you spend an hour in a day, or in a week, in praying
to your Father which is in secret? Yea, an hour in a month? Have you
spent one hour together in private prayer ever since you was born?
Ah poor Christian! Shall not the Pharisee rise up in the judgment
against thee and condemn thee? His righteousness is as far above
thine, as the heaven is above the earth.

9. The Pharisee, thirdly, paid tithes and gave alms of all that he
possest. And in how ample a manner? So that he was (as we phrase
it) “a man that did much good.” Do we come up to him here? Which
of us is so abundant as he was, in good works? Which of us gives a
fifth of all his substance to God? Both of the principal, and of the
increase? Who of us, out of (suppose) an hundred pounds a year,
gives twenty to God and the poor: out of fifty, ten; and so in a larger
or a smaller proportion? When shall our righteousness, in using all
the means of grace, in attending all the ordinances of God, in
avoiding evil and doing good, equal at least the righteousness of the
Scribes and Pharisees?

10. Although if it only equalled theirs, what would that profit? For
verily I say unto you except your righteousness shall exceed the
righteousness of the Scribes and Pharisees, ye shall in no case enter
into the kingdom of heaven. But how can it exceed theirs? Wherein
does the righteousness of a Christian exceed that of a Scribe or
Pharisee?

Christian righteousness exceeds theirs, first, in the extent of it.

Most of the Pharisees, though they were rigorously exact in many
things, yet were emboldened by the traditions of the elders to
dispense with others of equal importance. Thus they were extremely
punctual in keeping the fourth commandment; they would not even
rub an ear of corn on the sabbath day: But not at all in keeping the
third, making little account of light, or even false swearing. So that
their righteousness was partial: whereas the righteousness of a real
Christian is universal. He does not observe one, or some parts of the
law of God, and neglect the rest; but keeps all his commandments,
loves them all, values them above gold or precious stones.
 11. It may be indeed, that some of the Scribes and Pharisees,
endeavoured to keep all the commandments, and consequently
were, as touching the righteousness of the law, that is, according to
the letter of it, blameless. But still the righteousness of a Christian
exceeds all this righteousness of a Scribe or Pharisee, by fulfilling the
Spirit as well as the letter of the law, by inward as well as outward
obedience. In this, in the spirituality of it, it admits of no
comparison. This is the point which our Lord has so largely proved,
in the whole tenor of this discourse. Their righteousness was
external only: Christian righteousness is in the inner man. The
Pharisee cleansed the outside of the cup and the platter; the
Christian is clean within. The Pharisee laboured to present God with
a good life; the Christian with a holy heart. The one shook off the
leaves, perhaps the fruits of sin; the other lays the axe to the root:
as not being content with the outward form of godliness, how exact
soever it be, unless the life, the Spirit, the power of God unto
salvation, be felt in the inmost soul.

Thus, to do no harm, to do good, to attend the ordinances of

God, (the righteousness of a Pharisee) are all external: whereas, on
the contrary, poverty of spirit, mourning, meekness, hunger and
thirst after righteousness, the love of our neighbour, and purity of
heart, (the righteousness of a Christian) are all internal. And even
peace-making (or doing good) and suffering for righteousness sake,
stand intitled to the blessings annext to them, only as they imply
these inward dispositions, as they spring from, exercise and confirm
them. So that whereas the righteousness of the Scribes and
Pharisees was external only, it may be said, in some sense that the
righteousness of a Christian is internal only: all his actions and
sufferings being as nothing in themselves, being estimated before
God only by the tempers from which they spring.

12. *Whosoever therefore thou art, who bearest the holy and
venerable name of a Christian, see, first that thy righteousness fall
not short of the righteousness of the Scribes and Pharisees. Be not
thou as other men are. Dare to stand alone, to be
 “Against example, singularly good?”

If thou follow a multitude at all, it must be, to do evil. Let not

custom or fashion be thy guide; but reason and religion. The
practice of others is nothing to thee: every man must give an
account of himself to God. Indeed if thou canst save the soul of
another, do: but at least, save one, thy own. Walk not in the path of
death, because it is broad, and many walk therein. Nay, by this very
token thou mayest know it. Is the way wherein thou now walkest, a
broad, well-frequented, fashionable way? Then it infallibly leads to
destruction. O be not thou “damned for company:” cease from evil;
fly from sin as from the face of a serpent. At least, do no harm. He
that committeth sin is of the devil. Be not thou found in that number.
Touching outward sins, surely the grace of God is even now
sufficient for thee. Herein at least, exercise thyself to have a
conscience void of offence, toward God and toward man.

Secondly, Let not thy righteousness fall short of theirs, with

regard to the ordinances of God. If thy labour or bodily strength will
not allow of thy fasting twice in the week, however deal faithfully
with thy own soul, and fast as often as thy strength will permit. Omit
no public, no private opportunity, of pouring out thy soul in prayer.
Neglect no occasion of eating that bread and drinking that cup,
which is the communion of the body and blood of Christ. Be diligent
in searching the scriptures; read as thou mayest, and meditate
therein day and night. Rejoice to embrace every opportunity, of
hearing the word of reconciliation declared by the ambassadors of
Christ, the stewards of the mysteries of God. In using all the means
of grace, in a constant and careful attendance on every ordinance of
God, live up to (at least, till thou canst go beyond) the righteousness
of the Scribes and Pharisees.

Thirdly, Fall not short of a Pharisee in doing good. Give alms of

all thou dost possess. Is any hungry? Feed him. Is he a-thirst? Give
him drink. Naked? Cover him with a garment. If thou hast this
world’s goods, do not limit thy beneficence to a scanty proportion.
Be merciful to the uttermost of thy power. Why not, even as this
Pharisee? Now make thyself friends, while the time is, of the
mammon of unrighteousness, that when thou failest, when this
earthly tabernacle is dissolved, they may receive thee into
everlasting habitations.

13. But rest not here. Let thy righteousness exceed the
righteousness of the Scribes and Pharisees. Be not thou content, to
keep the whole law, and offend in one point. Hold thou fast all his
commandments, and all false ways do thou utterly abhor. Do all the
things, whatsoever he hath commanded, and that with all thy might.
Thou canst do all things through Christ strengthning thee, though
without him thou canst do nothing.

*Above all, let thy righteousness exceed theirs in the purity and
spirituality of it. What is the exactest form of religion to thee? The
most perfect outside righteousness? Go thou higher and deeper than
all this. Let thy religion be the religion of the heart. Be thou poor in
spirit; little and base and mean and vile in thy own eyes; amazed
and humbled to the dust at the love of God which is in Christ Jesus
thy Lord. Be serious: let the whole stream of thy thoughts, words
and works, be such as flows from the deepest conviction, that thou
standest on the edge of the great gulph, thou and all the children of
men, just ready to drop in, either into everlasting glory, or
everlasting burnings. Be meek: let thy soul be filled with mildness,
gentleness, patience, long-suffering toward all men: at the same
time that all which is in thee is a-thirst for God, the living God;
longing to awake up after his likeness, and to be satisfied with it. Be
thou a lover of God and of all mankind. In this spirit, do and suffer
all things. Thus exceed the righteousness of the Scribes and
Pharisees, and thou shalt be called great in the kingdom of heaven.
 SERMON XXVI.

UPON OUR LORD’S SERMON

ON THE MOUNT.
Discourse VI.
Matt. vi. 1‒15.
Take heed that ye do not your alms before men, to be seen
of them: otherwise ye have no reward of your Father
which is in heaven.

Therefore when thou dost thine alms, do not sound a

trumpet before thee, as the hypocrites do in the
synagogues and in the streets, that they may have
praise of men. Verily I say unto you, they have their
reward.

But when thou doest alms, let not thy left hand know what
thy right hand doth: that thine alms may be in secret,
and thy Father which seeth in secret, himself shall
reward thee openly.
 And when thou prayest, thou shalt not be as the hypocrites
are; for they love to pray, standing in the synagogues
and in the corners of the streets, that they may be
seen of men. Verily I say unto you, they have their
reward.

But thou when thou prayest, enter into thy closet, and
when thou hast shut the door, pray to thy Father which
is in secret; and thy Father which seeth in secret, he
shall reward thee openly.

But when ye pray, use not vain repetitions, as the Heathen

do; for they think that they shall be heard for their
much speaking.

Be not ye therefore like unto them: for your Father knoweth

what things ye have need of, before you ask him.

After this manner therefore pray ye: Our Father which art in
heaven, hallowed be thy name. Thy kingdom come.
Thy will be done on earth as it is in heaven. Give us
this day our daily bread. And forgive us our trespasses,
as we forgive them that trespass against us, and lead
us not into temptation, but deliver us from evil. For
thine is the kingdom and the power and the glory, for
ever and ever. Amen.

For if ye forgive men their trespasses, your heavenly Father

will also forgive you.

But if ye forgive not men their trespasses, neither will your

Father forgive your trespasses.

I
1. N the preceding chapter our Lord has described inward religion,
in its various branches. He has laid before us those dispositions
of soul, which constitute real Christianity: the inward tempers
contained in that holiness, without which no man shall see the Lord;
the affections which, when flowing from their proper fountain, from
a living faith in God thro’ Christ Jesus, are intrinsically and essentially
good, and acceptable to God. He proceeds to shew in this chapter,
how all our actions likewise, even those that are indifferent in their
own nature, may be made holy and good and acceptable to God, by
a pure and holy intention. Whatever is done without this, he largely
declares, is of no value before God. Whereas, whatever outward
works are thus consecrated to God, they are in his sight of great
price.

2. The necessity of this purity of intention, he shews first, with

regard to those, which are usually accounted religious actions, and
indeed are such, when performed with a right intention. Some of
these are commonly termed works of piety; the rest, works of
charity or mercy. Of the latter sort, he particularly names almsgiving;
of the former, prayer and fasting. But the directions given for these
are equally to be applied to every work, whether of charity or mercy.

I. 1. And first, with regard to works of mercy. Take heed, saith

he, that ye do not your alms before men, to be seen of them.
Otherwise ye have no reward of your Father which is in heaven. That
ye do not your alms. Altho’ this only is named, yet is every work of
charity included, every thing which we give, or speak, or do,
whereby our neighbour may be profited, whereby another man may
receive any advantage, either in his body or soul. The feeding the
hungry, the cloathing the naked, and entertaining or assisting the
stranger, the visiting those that are sick or in prison, the comforting
the afflicted; the instructing the ignorant, the reproving the wicked,
the exhorting and encouraging the well-doer; and if there be any
other work of mercy, it is equally included in this direction.

2. Take heed that ye do not your alms before men, to be seen of

them. The thing which is here forbidden, is not, barely the doing
good in the sight of men: this circumstance alone, that others see
what we do, makes the action neither worse nor better: but the
doing it before men, to be seen of them; with this view, from this
intention only. I say, from this intention only; for this may, in some
cases, be a part of our intention; we may design that some of our
actions should be seen, and yet they may be acceptable to God. We
may intend, that our light should shine before men, when our
conscience bears us witness, in the Holy Ghost, that our ultimate
end in designing they should see our good works, is, That they may
glorify our Father which is in heaven. But take heed that ye do not
the least thing with a view to your own glory. Take heed that a
regard to the praise of men, have no place at all in your works of
mercy. If ye seek your own glory, if you have any design to gain the
honour that cometh of men, whatever is done with this view is
nothing worth: it is not done unto the Lord: he accepteth it not; ye
have no reward for this of your Father which is in heaven.

3. Therefore when thou dost thine alms, do not sound a trumpet

before thee, as the hypocrites do, in the synagogues and in the
streets, that they may have praise of men. The word synagogue
does not here mean, a place of worship, but any place of public
resort, such as the market-place or exchange. It was a common
thing among the Jews, who were men of large fortunes, particularly
among the Pharisees, to cause a trumpet to be sounded before them
in the most public parts of the city, when they were about to give
any considerable alms. The pretended reason for this was, to call the
poor together to receive it: but the real design, that they might have
praise of men. But be not thou like unto them. Do not thou cause a
trumpet to be sounded before thee. Use no ostentation in doing
good. Aim at the honour which cometh of God only. They who seek
the praise of men, have their reward. They shall have no praise of
God.

4. But when thou doest alms, let not thy left hand know what thy
right hand doth. This is a proverbial expression, the meaning of
which is, do it in as secret a manner as is possible: as secret as is
consistent with the doing it at all; (for it must not be left undone:
omit no opportunity of doing good, whether secretly or openly) and
with the doing it in the most effectual manner. For here is also an
exception to be made. When you are fully persuaded in your own
mind, that by your not concealing the good which is done, either you
will yourself be enabled, or others excited to do the more good, then
you may not conceal it: then let your light appear, and shine to all
that are in the house. But unless where the glory of God and the
good of mankind oblige you to the contrary, act in as private and
unobserved a manner, as the nature of the thing will admit: that thy
alms may be in secret, and thy Father which seeth in secret, he shall
reward thee openly. Perhaps in the present world; many instances of
this stands recorded in all ages: but infallibly in the world to come,
before the general assembly of men and angels.

II. 1. From works of charity or mercy, our Lord proceeds to those

which are termed works of piety. And when thou prayest, saith he,
thou shalt not be as the hypocrites are: for they love to pray
standing in the synagogues, and in the corners of the streets, that
they may be seen of men. Thou shalt not be as the hypocrites are.
Hypocrisy then, or insincerity, is the first thing we are to guard
against in prayer. Beware not to speak what thou dost not mean.
Prayer is, the lifting up of the heart to God: all words of prayer
without this are mere hypocrisy. Whenever therefore thou
attemptest to pray, see that it be thy one design, to commune with
God, to lift up thy heart to him, to pour out thy soul before him. Not
as the hypocrites, who love, or are wont, to pray standing in the
synagogues, the exchange or market-places, and in the corners of
the streets, wherever the most people are, that they may be seen of
men: this was the sole design, the motive and end, of the prayers
which they there repeated. Verily I say unto you, they have their
reward. They are to expect none from your Father which is in
heaven.

2. But it is not only, the having an eye to the praise of men,

which cuts us off from any reward in heaven; which leaves us no
room to expect the blessing of God, upon our works whether of
piety or mercy. Purity of intention is equally destroyed by a view to
any temporal reward whatever. If we repeat our prayers, if we
attend the public worship of God, if we relieve the poor, with a view
to gain or interest, it is not a whit more acceptable to God, than if it
were done with a view to praise. Any temporal view, any motive
whatever on this side eternity, any design but that of promoting the
glory of God, and the happiness of men, for God’s sake, makes every
action, however fair it may appear to men, an abomination unto the
Lord.

3. But when thou prayest, enter into thy closet, and when thou
hast shut the door, pray to thy Father which is in secret. There is a
time, when thou art openly to glorify God, to pray and praise him in
the great congregation. But when thou desirest more largely and
more particularly to make thy requests known unto God, whether it
be in the evening or in the morning or at noon-day, enter into thy
closet and shut the door. Use all the privacy thou canst. (Only leave
it not undone, whether thou hast any closet, any privacy or no. Pray
to God if it be possible, when none seeth but he: but if otherwise,
pray to God.) Thus pray to thy Father which is in secret; pour out all
thy heart before him. And thy Father which is in secret, he shall
reward thee openly.

4. But when ye pray, even in secret, use not vain repetitions, as

the Heathen do. μὴ βαττολογήσητε. Do not use abundance of words
without any meaning. Say not the same thing over and over again:
think not the fruit of your prayers depends on the length of them:
like the Heathens; for they think they shall be heard for their much
speaking.

The thing here reproved, is not simply the length, any more than
the shortness of our prayers: but, first, length without meaning; the
speaking much, and meaning little or nothing: the using (not all
repetitions; for our Lord himself prayed thrice, repeating the same
words; but) vain repetitions, as the Heathens did, reciting the names
of their Gods over and over: as they do among Christians, (vulgarly
so called) and not among the papists only, who say over and over
the same string of prayers, without ever feeling what they speak:
secondly, the thinking to be heard for our much speaking, the
fancying God measures prayers by their length, and is best pleased
with those which contain the most words, which sound the longest
in his ears. These are such instances of superstition and folly, as all
who are named by the name of Christ, should leave to the Heathens,
to them on whom the glorious light of the gospel hath never shined.

5. Be not ye therefore like unto them. Ye who have tasted of the

grace of God in Christ Jesus, are throughly convinced, your Father
knoweth what things ye have need of before ye ask him. So that the
end of your praying, is not to inform God, as tho’ he knew not your
wants already; but rather to inform yourselves, to fix the sense of
those wants more deeply in your hearts, and the sense of your
continual dependence on him, who only is able to supply all your
wants. It is not so much to move God, who is always more ready to
give than you to ask; as to move yourselves, that you may be willing
and ready to receive, the good things he has prepared for you.

III. 1. After having taught the true nature and ends of prayer, our
Lord subjoins an example of it: even that divine form of prayer,
which seems in this place to be proposed by way of pattern chiefly,
as the model and standard of all our prayers: After this manner
therefore pray ye. Whereas elsewhere he enjoins the use of these
very words, 97He said unto them, when ye pray, say――

2. *We may observe in general concerning this divine prayer.

First, that it contains all we can reasonably or innocently pray for.
There is nothing which we have need to ask of God, nothing which
we can ask without offending him, which is not included either
directly or indirectly in this comprehensive form: secondly, that it
contains all we can reasonably or innocently desire; whatever is for
the glory of God, whatever is needful or profitable not only for
ourselves, but for every creature in heaven and earth. And indeed
our prayers are the proper test of our desires; nothing being fit to
have a place in our desires, which is not fit to have a place in our
prayers: what we may not pray for, neither should we desire: thirdly,
that it contains all our duty to God and man: whatsoever things are
pure and holy, whatsoever God requires of the children of men,
whatsoever is acceptable in his sight, whatsoever it is whereby we
may profit our neighbour, being exprest or implied therein.

3. It consists of three parts, the preface, the petitions, and the

doxology or conclusion. The preface, Our Father which art in
Heaven, lays a general foundation for prayer; comprizing what we
must first know of God, before we can pray, in confidence of being
heard. It likewise points out to us all those tempers, with which we
are to approach to God, which are most essentially requisite, if we
desire either our prayers or our lives should find acceptance with
him.

4. “Our Father.” If he is a father, then he is good, then he is

loving to his children. And here is the first and great reason for
prayer. God is willing to bless, let us ask for a blessing. “Our
Father,”—Our Creator: the author of our being; he who raised us
from the dust of the earth, who breathed into us the breath of life,
and we became living souls. But if he made us, let us ask and he will
not with-hold, any good thing from the work of his own hands. “Our
Father”—Our preserver; who day by day sustains the life he has
given: of whose continuing love we now and every moment receive
life and breath and all things. So much the more boldly let us come
to him, and we shall find mercy and grace to help in time of need.
Above all, the Father of our Lord Jesus Christ, and of all that believe
in him: who justifies us freely by his grace, through the redemption
that is in Jesus: who hath blotted out all our sins, and healed all our
infirmities; who hath received us for his own children, by adoption
and grace, and because we are sons, hath sent forth the Spirit of his
Son into our hearts, crying, Abba, Father: who hath begotten us
again of incorruptible seed, and created us a-new in Christ Jesus.
Therefore we know that he heareth us always: therefore we pray to
him without ceasing. We pray, because we love. And we love him,
because he first loved us.
 5. “Our Father”—Not mine only who now cry unto him; but our’s,
in the most extensive sense. The God and Father of the Spirits of all
flesh; the Father of angels and men: (so the very Heathens
acknowledged him to be, Πατήρ ἀνδρῶν τε θεῶν τε·) The Father of
the universe, of all the families both in heaven and earth. Therefore
with him there is no respect of persons. He loveth all that he hath
made. He is loving unto every man, and his mercy is over all his
works. And the Lord’s delight is in them that fear him, and put their
trust in his mercy; in them that trust in him thro’ the Son of his love,
knowing they are accepted in the Beloved. But if God so loved us,
we ought also to love one another. Yea, all mankind: seeing God so
loved the world, that he gave his only begotten Son, even to die the
death, that they might not perish but have everlasting life.

6. Which art in heaven:—high and lifted up; God over all, blessed
for ever. Who sitting on the circle of the heavens, beholdeth all
things both in heaven and earth. Whose eye pervades the whole
sphere of created being; yea and of uncreated night: unto whom are
known all his works, and all the works of every creature, not only
from the beginning of the world (a poor, low, weak translation) but
ἀπ᾽ αἰῶνος· from all eternity, from everlasting to everlasting: who
constrains the host of heaven, as well as the children of men, to cry
out with wonder and amazement, O the depth! The depth of the
riches both of the wisdom and of the knowledge of God! Which art in
heaven—the Lord and ruler of all, superintending and disposing all
things: who art the King of Kings, and Lord of Lords, the blessed and
only Potentate: who art strong and girded about with power, doing
whatsoever pleaseth thee! The Almighty: for whensoever thou
willest, to do is present with thee. In heaven,—eminently there.
Heaven is thy throne, the place where thine honour particularly
dwelleth. But not there alone; for thou fillest heaven and earth, the
whole expanse of space. Heaven and earth are full of thy glory.
Glory be to thee, O Lord most high!

Therefore should we serve the Lord with fear, and rejoice unto
him with reverence. Therefore should we think, speak and act, as
continually under the eye, in the immediate presence of the Lord,
the King.

7. *Hallowed be thy name. This is the first of the six petitions,

whereof the prayer itself is composed. The name of God is God
himself; the nature of God, so far as it can be discovered to man: it
means therefore, together with his existence, all his attributes or
perfections—his eternity, particularly signified by his great and
incommunicable name Jehovah, as the apostle John translates it, τὸ
ἀ, καὶ τὸ ω, ἀρχὴ καὶ τέλος. ὁ ὤν καὶ ὁ ἦν καὶ ὁ ἐρχόμενος· The
alpha and omega, the beginning and the end, he which is, and
which was, and which is to come:—His fulness of being, denoted by
his other great name, I am that I am—His omnipresence—His
omnipotence; who is indeed the only agent in the material world; all
matter being essentially dull and inactive, and moving only as it is
moved by the finger of God: and he is the spring of action in every
creature, visible and invisible; which could neither act nor exist,
without the continued influx and agency of his almighty power—His
wisdom, clearly deduced from the things that are seen, from the
goodly order of the universe—His trinity in unity and unity in trinity,
discovered to us in the very first line of his written word ‫‏ברא אלהים‬‎:
literally the Gods created, a plural noun joined with a verb of the
singular number: as well as in every part of his subsequent
revelations, given by the mouth of all his holy prophets and apostles
—His essential purity and holiness—and above all, his love, which is
the very brightness of his glory.

In praying that God, or his name may be hallowed or glorified,

we pray that he may be known, such as he is, by all that are capable
thereof, by all intelligent beings, and with affections suitable to that
knowledge: that he may be duly honoured and feared and loved by
all in heaven above and in the earth beneath; by all angels and men,
whom for that end he has made capable of knowing and loving him
to eternity.
 8. Thy kingdom come. This has a close connexion with the
preceding petition. In order that the name of God might be hallowed
we pray that his kingdom, the kingdom of Christ may come. This
kingdom then comes to a particular person, when he repents and
believes the gospel: when he is taught of God, not only to know
himself, but to know Jesus Christ and him crucified. As this is life
eternal, to know the only true God, and Jesus Christ whom he hath
sent, so it is the kingdom of God begun below, set up in the
believer’s heart: the Lord God omnipotent then reigneth, when he is
known through Christ Jesus. He taketh unto himself his mighty
power; that he may subdue all things unto himself. He goeth on in
the soul conquering and to conquer, ’till he hath put all things under
his feet, ’till every thought is brought into captivity to the obedience
of Christ.

When therefore God shall give his Son the Heathen for his
inheritance, and the utmost parts of the earth for his possession;
when all kingdoms shall bow before him, and all nations shall do him
service; when the mountain of the Lord’s house, the church of Christ
shall be established in the top of the mountains; when the fullness
of the Gentiles shall come in, and all Israel shall be saved: then shall
it be seen, that the Lord is King and hath put on glorious apparel,
appearing to every soul of man, as King of Kings, and Lord of Lords.
And it is meet for all those who love his appearing, to pray that he
would hasten the time: that this his kingdom, the kingdom of grace
may come quickly, and swallow up all the kingdoms of the earth;
that all mankind receiving him for their king, truly believing in his
name, may be filled with righteousness and peace and joy, with
holiness and happiness, ’till they are removed hence into his
heavenly kingdom, there to reign with him for ever and ever.

For this also we pray in those words, Thy kingdom come: we

pray for the coming of his everlasting kingdom, the kingdom of glory
in heaven, which is the continuation and perfection of the kingdom
of grace an earth. Consequently this, as well as the preceding
petition, is offered up for the whole intelligent creation, who are all
interested in this grand event, the final renovation of all things, by
God’s putting an end to misery and sin, to infirmity and death, taking
all things into his own hands, and setting up the kingdom which
endureth throughout all ages.

Exactly answerable to this, are those awful words, in the prayer,

at the burial of the dead; “Beseeching thee, that it may please thee
of thy gracious goodness, shortly to accomplish the number of thine
elect, and to hasten thy kingdom: that we with all those that are
departed, in the true faith of thy holy name, may have our perfect
consummation and bliss, both in body and soul, in thy everlasting
glory.”

9. Thy will be done on earth as it is in heaven. This is the

necessary and immediate consequence, wherever the kingdom of
God is come: wherever God dwells in the soul by faith, and Christ
reigns in the heart by love.

It is probable, many, perhaps the generality of men, at the first

view of these words, are apt to imagine, they are only an expression
of, or petition for resignation; for a readiness to suffer the will of
God, whatsoever it be concerning us. And this is unquestionably a
divine and excellent temper, a most precious gift of God. But this is
not what we pray for in this petition, at least not in the chief and
primary sense of it. We pray, not so much for a passive, as for an
active conformity to the will of God, in saying, Thy will be done on
earth as it is done in heaven.

*How is it done by the angels of God in heaven? Those who now

circle his throne rejoicing? They do it willingly; they love his
commandments, and gladly hearken to his words. It is their meat
and drink to do his will; it is their highest glory and joy. They do it
continually; there is no interruption in their willing service. They rest
not day nor night, but employ every hour (speaking after the
manner of men; otherwise our measures of duration, days and
nights and hours, have no place in eternity) in fulfilling his
commands, in executing his designs, in performing the council of his
will. And they do it perfectly. No sin, no defect belongs to angelick
minds. It is true, the stars are not pure in his sight, even the
morning-stars that sing together before him. In his sight, that is in
comparison of him, the very angels are not pure. But this does not
imply, that they are not pure in themselves. Doubtless they are; they
are without spot and blameless. They are altogether devoted to his
will, and perfectly obedient in all things.

*If we view this in another light, we may observe, the angels of

God in heaven, do all the will of God. And they do nothing else,
nothing but what they are absolutely assured is his will. Again, they
do all the will of God, as he willeth, in the manner which pleases
him, and no other. Yea, and they do this, only because it is his will;
for this end and no other reason.

10. When therefore we pray, that the will of God may be done on
earth as it is in heaven, the meaning is, that all the inhabitants of
the earth, even the whole race of mankind, may do the will of their
Father which is in heaven, as willingly as the holy angels: that these
may do it continually even as they, without any interruption of their
willing service: yea, and that they may do it perfectly; that the God
of peace, through the blood of the everlasting covenant, may make
them perfect in every good work to do his will, and work in them all
which is well-pleasing in his sight.

In other words, we pray, that we and all mankind, may do the

whole will of God in all things: and nothing else, not the least thing
but what is the holy and acceptable will of God. We pray that we
may do the whole will of God as he willeth, in the manner that
pleases him: and lastly, that we may do it, because it is his will: that
this may be the sole reason and ground, the whole and only motive
of whatsoever we think, or whatsoever we speak or do.

11. Give us this day our daily bread. In the three former
petitions, we have been praying for all mankind. We come now more
particularly to desire a supply for our own wants. Not that we are
directed even here, to confine our prayer altogether to ourselves:
but this and each of the following petitions may be used for the
whole church of Christ upon earth.

By bread we may understand, all things needful whether for our

souls or bodies: τὰ πρὸς ζωὴν καὶ εὐσέβειαν· the things pertaining to
life and godliness. We understand not barely the outward bread,
what our Lord terms the meat which perisheth; but much more the
spiritual bread, the grace of God, the food which endureth unto
everlasting life. It was the judgment of many of the antient fathers,
that we are here to understand, the sacramental bread also: daily
received in the beginning by the whole church of Christ, and highly
esteemed ’till the love of many waxed cold, as the grand channel
whereby the grace of his Spirit was conveyed to the souls of all the
children of God.

Our daily bread. The word we render daily has been differently
explained by different commentators. But the most plain and natural
sense of it seems to be this, which is retained in almost all
translations, as well antient as modern: what is sufficient for this
day; and so for each day, as it succeeds.

12. Give us. For we claim nothing of right, but only of free mercy.
We deserve not the air we breathe, the earth that bears, or the sun
that shines upon us. All our desert, we own, is hell. But God loves us
freely. Therefore we ask him to give, what we can no more procure
for ourselves, than we can merit it at his hands.

Not that either the goodness or the power of God is a reason for
us to stand idle. It is his will, that we should use all diligence in all
things, that we should employ our utmost endeavours, as much as if
our success were the natural effect of our own wisdom and strength.
And then, as tho’ we had done nothing, we are to depend on him,
the giver of every good and perfect gift.
 *This day. For we are to take no thought for the morrow. For this
very end has our wise Creator divided life into these little portions of
time, so clearly separated from each other: that we might look on
every day, as a fresh gift of God, another life, which we may devote
to his glory; and that every evening may be as the close of life,
beyond which we are to see nothing but eternity.

13. And forgive us our trespasses, as we forgive them that

trespass against us. As nothing but sin can hinder the bounty of God
from flowing forth upon every creature, so this petition naturally
follows the former; that all hindrances being removed, we may the
more clearly trust in the God of love, for every manner of thing
which is good.

Our trespasses. The word properly signifies our debts. Thus our
sins are frequently represented in scripture: every sin laying us
under a fresh debt to God; to whom we already owe, as it were, ten
thousand talents. What then can we answer when he shall say, Pay
me that thou owest? We are utterly insolvent: we have nothing to
pay: We have wasted all our substance. Therefore if he deal with us
according to the rigour of his law, if he exact what he justly may, he
must command us to be bound hand and foot, and delivered over to
the tormentors.

Indeed we are already bound hand and foot, by the chains of our
own sins. These, considered with regard to ourselves, are chains of
iron and fetters of brass. They are wounds wherewith the world, the
flesh and the devil, have gashed and mangled us all over. They are
diseases that drink up our blood and spirits, that bring us down to
the chambers of the grave. But considered, as they are here, with
regard to God, they are debts immense and numberless. Well
therefore, seeing we have nothing to pay, may we cry unto him, that
he would frankly forgive us all.

The word translated forgive, implies either to forgive a debt, or to

unloose a chain. And if we attain the former, the latter follows of
course; if our debts are forgiven, the chains fall off our hands. As
soon as ever, through the free grace of God in Christ, we receive
forgiveness of sins, we receive likewise a lot among those which are
sanctified, by faith which is in him. Sin has lost its power: it has no
dominion over those, who are under grace, that is, in favour with
God. As there is now no condemnation for them that are in Christ
Jesus, so they are freed from sin as well as from guilt. The
righteousness of the law is fulfilled in them, and they walk not after
the flesh but after the Spirit.

14. As we forgive them that trespass against us. In these words

our Lord clearly declares, both on what condition, and in what
degree or manner we may look to be forgiven of God. All our
trespasses and sins are forgiven us, if we forgive and as we forgive
others. This is a point of the utmost importance. And our blessed
Lord is so jealous, lest at any time we should let it slip out of our
thoughts, that he not only inserts it in the body of his prayer, but
presently after repeats it twice over. If, saith he, ye forgive men their
trespasses, your heavenly Father will also forgive you. But if ye
forgive not men their trespasses, neither will your Father forgive
your trespasses. Secondly, God forgives us, as we forgive others.
*So that if any malice or bitterness, if any taint of unkindness or
anger remains, if we do not clearly, fully, and from the heart, forgive
all men their trespasses, we so far cut short the forgiveness of our
own. God cannot clearly and fully forgive us. He may shew us some
degree of mercy. But we will not suffer him to blot out all our sins,
and forgive all our iniquities.

In the mean time, while we do not from our hearts, forgive our
neighbour his trespasses, what manner of prayer are we offering to
God, whenever we utter these words? We are indeed setting God at
open defiance: we are daring him to do his worst. Forgive us our
trespasses, as we forgive them that trespass against us! That is in
plain terms, “Do not thou forgive us at all: we desire no favour at
thy hands. We pray, that thou wilt keep our sins in remembrance,
and that thy wrath may abide upon us.” But can you seriously offer
such a prayer to God? And hath he not yet cast you quick into hell?
O tempt him no longer! Now, even now, by his grace, forgive as you
would be forgiven! Now have compassion on thy fellow-servant, as
God hath had and will have pity on thee.

15. And lead us not into temptation, but deliver us from evil.
Lead us not into temptation. The word translated temptation, means
trial of any kind. And so the English word temptation was formerly
taken, in an indifferent sense: although now it is usually understood,
of solicitation to sin. St. James uses the word in both these senses;
first, in its general, then in its restrained acceptation. He takes it in
the former sense when he saith, 98Blessed is the man that endureth
temptation; for when he is tried, or approved of God, he shall
receive the crown of life. He immediately adds, taking the word in
the latter sense, Let no man say when he is tempted, I am tempted
of God: for God cannot be tempted with evil, neither tempteth he
any man. But every man is tempted, when he is drawn away of his
own lust, or desire, ἐξελκόμενος, drawn out of God, in whom alone
he is safe, and enticed, caught as a fish with a bait. Then it is, when
he is thus drawn away and enticed, that he properly enters into
temptation. The temptation covers him as a cloud: it overspreads his
whole soul. Then how hardly shall he escape out of the snare?
Therefore we beseech God, not to lead us into temptation, that is
(seeing God tempteth no man) not to suffer us to be led into it. But
deliver us from evil: rather, from the evil one; ἀπὸ τοῦ πονηροῦ. Ὁ
Πονηρός is unquestionably the wicked one, emphatically so called,
the prince and god of this world, who works with mighty power in
the children of disobedience. But all those who are the children of
God by faith, are delivered out of his hands. He may fight against
them: and so he will. But he cannot conquer, unless they betray
their own souls. He may torment for a time; but he cannot destroy;
for God is on their side, who will not fail in the end, to avenge his
own elect, that cry unto him, day and night, “Lord, when we are
tempted, suffer us not to enter into temptation. Do thou make a way
for us to escape, that the wicked one touch us not.”
 16. The conclusion of this divine prayer, commonly called the
doxology, is a solemn thanksgiving, a compendious
acknowledgement of the attributes and works of God. For thine is
the kingdom; the sovereign right of all things that are, or ever were
created: yea, thy kingdom is an everlasting kingdom, and thy
dominion endureth throughout all ages. The power: The executive
power, whereby thou governest all things in thy everlasting kingdom,
whereby thou dost whatsoever pleaseth thee, in all places of thy
dominion.—And the glory; the praise due from every creature, for
thy power and the mightiness of thy kingdom, and for all thy
wondrous works, which thou workest from everlasting, and shalt do,
world without end, for ever and ever! Amen. So be it!

I believe it will not be unacceptable to the serious reader, to

subjoin

A Paraphrase on the Lord’s Prayer.

F ATHER of all, whose powerful voice,

Call’d forth this universal frame,

Whose mercies over all rejoice,

Thro’ endless ages still the same.

Thou by thy word upholdest all;

Thy bounteous Love to all is shew’d,

Thou hearest thy every creature call,

And fillest every mouth with good.

In heaven thou reign’st, enthron’d in light,

Nature’s expanse beneath thee spread;

Earth, air, and sea before thy sight,

And hell’s deep gloom are open laid.

Wisdom, and might, and love are thine;

Prostrate before thy face we fall,

Confess thine attributes divine,

And hail the sovereign Lord of all.

Thee, sovereign Lord, let all confess,

That moves in earth, or air, or sky,

Revere thy power, thy goodness bless,

Tremble before thy piercing eye.

All ye who owe to him your birth,

In praise your every hour employ:

Jehovah reigns! Be glad, O earth,

And shout ye morning-stars, for joy.

Son of thy Sire’s eternal love,

Take to thyself thy mighty power;

Let all earth’s sons thy mercy prove,

Let all thy bleeding grace adore.

The triumphs of thy love display;

In every heart reign thou alone;

’Till all thy foes confess thy sway,

And glory ends what grace begun.

Spirit of grace, and health, and power,

Fountain of light and love below,

Abroad thine healing influence shower,

O’er all the nations let it flow.

Inflame our hearts with perfect love,

In us the work of faith fulfil:

So not heaven’s host shall swifter move

Than we on earth to do thy will.

Father, ’tis thine each day to yield

Thy children’s wants a fresh supply;

Thou cloth’st the lillies of the field,

And hearest the young ravens cry.

On thee we cast our care; we live

Thro’ thee, who know’st our every need;

O feed us with thy grace, and give

Our souls this day the living bread.

Eternal, spotless Lamb of God,

Before the world’s foundation slain,

Sprinkle us ever with thy blood,

O cleanse and keep us ever clean.

To every soul (all praise to thee)

Our bowels of compassion move:

And all mankind by this may see

God is in us; for God is love.

Giver and Lord of life, whose power

And guardian care for all are free;

To Thee in fierce temptation’s hour,

From sin and Satan let us flee.

Thine, Lord, we are, and ours thou art;

In us be all thy goodness shew’d;

Renew, enlarge, and fill our heart

With peace and joy and heaven and God.

Blessing and honour, praise and love,

Co-equal, Co-eternal, Three,

In earth below, in heaven above,

By all thy works be paid to thee.

Thrice holy, thine the kingdom is,

The power omnipotent is thine;

And when created nature dies,

Thy never-ceasing glories shine.