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 A Textbook of
Physical Chemistry
Volume I
A Textbook of Physical Chemistry

Volume I :
States of Matter and Ions in Solution
Volume II :
Thermodynamics and Chemical Equilibrium
Volume III :
Applications of Thermodynamics
Volume IV :
Quantum Chemistry, Molecular Spectroscopy and Molecular Symmetry
Volume V :
Dynamics of Chemical Reactions, Statistical Thermodynamics, Macromolecules, and
Irreversible Processes
Volume VI : Computational Aspects in Physical Chemistry
 A Textbook of
Physical Chemistry
Volume I
(SI Units)

States of Matter and Ions in Solution

Fifth Edition

k l kAPoor
Former Associate Professor
Hindu College
University of Delhi
New Delhi

McGraw Hill Education (India) Private Limited

New Delhi

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Published by McGraw Hill Education (India) Private Limited,
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A Textbook of Physical Chemistry, Vol 1
Copyright © 2015 by McGraw Hill Education (India) Private Limited.
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Typeset at Script Makers, 19, A1-B, DDA Market, Paschim Vihar, New Delhi 110 063, and text printed at
To the memory of
my parents
Preface
In recent years, the teaching curriculum of Physical Chemistry in many Indian
universities has been restructured with a greater emphasis on a theoretical and
conceptual methodology and the applications of the underlying basic concepts and
principles. This shift in the emphasis, as I have observed, has unduly frightened
undergraduates whose performance in Physical Chemistry has been otherwise
generally far from satisfactory. This poor performance is partly because of the
non-availability of a comprehensive textbook which also lays adequate stress on
the logical deduction and solution of numericals and related problems. Naturally,
the students find themselves unduly constrained when they are forced to refer
to various books to collect the necessary reading material.

It is primarily to help these students that I have ventured to present a

textbook which provides a systematic and comprehensive coverage of the theory
as well as of the illustration of the applications thereof.
The present volumes grew out of more than a decade of classroom teaching
through lecture notes and assignments prepared for my students of BSc (General)
and BSc (Honours). The schematic structure of the book is assigned to cover
the major topics of Physical Chemistry in six different volumes. Volume I
discusses the states of matter and ions in solutions. It comprises five chapters
on the gaseous state, physical properties of liquids, solid state, ionic equilibria
and conductance. Volume II describes the basic principles of thermodynamics
and chemical equilibrium in seven chapters, viz., introduction and mathematical
background, zeroth and first laws of thermodynamics, thermochemistry, second
law of thermodynamics, criteria for equilibrium and A and G functions, systems
of variable composition, and thermodynamics of chemical reactions. Volume
III seeks to present the applications of thermodynamics to the equilibria
between phases, colligative properties, phase rule, solutions, phase diagrams of
one-, two- and three-component systems, and electrochemical cells. Volume
IV deals with quantum chemistry, molecular spectroscopy and applications of
molecular symmetry. It focuses on atomic structure, chemical bonding, electrical
and magnetic properties, molecular spectroscopy and applications of molecular
symmetry. Volume V covers dynamics of chemical reactions, statistical and
irreversible thermodynamics, and macromolecules in six chapters, viz., adsorption,
chemical kinetics, photochemistry, statistical thermodynamics, macromolecules
and introduction to irreversible processes. Volume VI describes computational
aspects in physical chemistry in three chapters, viz., synopsis of commonly used
statements in BASIC language, list of programs, and projects.
The study of Physical Chemistry is incomplete if students confine themselves
to the ambit of theoretical discussions of the subject. They must grasp the
practical significance of the basic theory in all its ramifications and develop a
clear perspective to appreciate various problems and how they can be solved.
viii Contents

It is here that these volumes merit mention. Apart from having a lucid style
and simplicity of expression, each has a wealth of carefully selected examples
and solved illustrations. Further, three types of problems with different objectives
in view are listed at the end of each chapter: (1) Revisionary Problems, (2) Try
Yourself Problems, and (3) Numerical Problems. Under Revisionary Problems,
only those problems pertaining to the text are included which should afford
an opportunity to the students in self-evaluation. In Try Yourself Problems,
the problems related to the text but not highlighted therein are provided. Such
problems will help students extend their knowledge of the chapter to closely
related problems. Finally, unsolved Numerical Problems are pieced together for
students to practice.
Though the volumes are written on the basis of the syllabi prescribed for
undergraduate courses of the University of Delhi, they will also prove useful to
students of other universities, since the content of physical chemistry remains
the same everywhere. In general, the SI units (Systeme International d’ unite’s),
along with some of the common non-SI units such as atm, mmHg, etc., have
been used in the books.

Salient Features

∑ Comprehensive coverage given to gaseous state, physical properties of liquids,

the solid state, physical properties of liquids, ionic equilibria and conductance
∑ Emphasis given to applications and principles
∑ Explanation of equations in the form of solved problems and numericals
∑ IUPAC recommendations and SI units have been adopted throughout
∑ Rich and illustrious pedagogy

Acknowledgements

I wish to acknowledge my greatest indebtedness to my teacher, late Prof. R P

Mitra, who instilled in me the spirit of scientific inquiry. I also record my sense
of appreciation to my students and colleagues at Hindu College, University
of Delhi, for their comments, constructive criticism and valuable suggestions
towards improvement of the book. I am grateful to late Dr Mohan Katyal
(St. Stephen’s College), and late Prof. V R Shastri (Ujjain University) for the
numerous suggestions in improving the book. I would like to thank Sh. M M
Jain, Hans Raj College, for his encouragement during the course of publication
of the book.
I wish to extend my appreciation to the students and teachers of Delhi
University for the constructive suggestions in bringing out this edition of the
book. I also wish to thank my children, Saurabh-Urvashi and Surabhi-Jugnu,
for many useful suggestions in improving the presentation of the book.
Finally, my special thanks go to my wife, Pratima, for her encouragement,
patience and understanding.
Feedback Request

The author takes the entire responsibility for any error or ambiguity, in fact or
opinion, that may have found its way into this book. Comments and criticism
from readers will, therefore, be highly appreciated and incorporated in subsequent
editions.
k l kapoor

Publisher’s Note

McGraw-Hill Education (India) invites suggestions and comments from you, all
of which can be sent to [email protected] (kindly mention the title
and author name in the subject line).
Piracy-related issues may also be reported.
 Contents

Preface vii
Acknowledgements viii

1. GASEoUS STATE 1

1.1 The Three States of Matter 1

1.2 Experimentally Derived Gas Laws 2
1.3 Equation of State 5
1.4 Application of Equation of State 7
1.5 Concepts of Partial Pressure and Partial Volume 12
1.6 The Kinetic Gas Equation 14
1.7 Some Derivation from the Kinetic Gas Equation 17
1.8 Real Gases 20
1.9 Van Der Waals Equation of State for a Real Gas 23
1.10 Other Equations of State for Real Gases 29
1.11 Reduction of Van Der Waals Equation to Virial Equation 31
1.12 Critical Constants 35
1.13 Continuity of State 38
1.14 Isotherms of Van Der Waals Equation 39
1.15 The Law of Corresponding States 44
1.16 Maxwellian Distribution of Molecular Speeds 50
1.17 Derivation of Some Expressions from the Maxwell Distribution 54
1.18 Barometric Distribution Law 60
1.19 Molecular Collisions in a Gas 66
1.20 Viscosity 71
1.21 Self Diffusion and Effusion Processes 75
1.22 Thermal Conductivity 79
1.23 Electrical Conductivity 81
1.24 Law of Equipartition of Energy 82
1.25 Degress of Freedom and the Average Energy of a Molecule 84
1.26 Heat Capacities 86
1.27 Comparison of Theoretical and Experimental Heat Capacities 88

2. PHYSICAl ProPErTIES oF lIQUIDS 105

2.1 Introduction 105

2.2 Vapour Pressure 105
2.3 Viscosity 114
2.4 Surface Tension 119
xii Contents

3. THE SolID STATE 132

3.1 Introduction 132

3.2 Faces, Edges and Interfacial Angle of a Crystal 132
3.3 Haüy’s Idea and Space Lattice 133
3.4 Crystal Systems 134
3.5 The Fourteen Bravais Lattices 137
3.6 Point Groups 141
3.7 Space Groups 142
3.8 Crystal Cleavage and Development of Its Faces 143
3.9 Designation of Planes 145
3.10 Interplanar Distances for Cubic Systems 148
3.11 Diffraction of Electromagnetic Radiation 150
3.12 Diffraction of X-rays by Crystals 152
3.13 Bragg’s Equation 153
3.14 Powder Method 156
3.15 Diffraction Pattern of a Cubic System 158
3.16 Crystal Structure of Sodium Chloride 163
3.17 Crystal Structure of Potassium Chloride 166
3.18 Density of Cubic Crystals 167
3.19 Classification of Crystals Based on Bond Type 171
3.20 General Discussion on Structure of Liquids 200
Annexure I: Symmetry Elements and Symmetry Operations 212
Annexure II: Supplementary Materials 218

4. IoNIC EQUIlIBrIA 231

4.1 The Dissolution Process 231

4.2 Classification of Substances 234
4.3 The Arrhenius Theory of Dissociation 235
4.4 Effect of Dilution on Degree of Dissociation 237
4.5 Dissociation of Pure Water 238
4.6 The pH-Scale 240
4.7 Classification of Acids and Bases in Water 242
4.8 Exact Treatment for lonization of a Monoprotic Acid 242
4.9 Exact Treatment for lonization of a Base 253
4.10 Exact Treatment for lonization of a Diprotic Acid 256
4.11 Dissociation of Polyprotic Acid 263
4.12 Solutions of Salts in Water: Hydrolysis 266
4.13 Exact Treatment of Hydrolysis of Salt Formed from a Weak Acid
and a Strong Base 268
4.14 Exact Treatment of Hydrolysis of Salt Formed from a Strong Acid
and a Weak Base 274
4.15 Exact Treatment of Hydrolysis of Salt Formed from a Weak Acid
and a Weak Base 277
 Contents xiii

4.16 Exact Treatment of Hydrolysis of Salt Involving Weak Conjugate Cation

and an Amphiprotic Anion 282
4.17 Exact Treatment of Hydrolysis of Salt Involving Strong Conjugate Cation
and Amphiprotic Anion 285
4.18 Hydrolysis of a Salt Containing Multivalent Cation or Anion 288
4.19 Exact Treatment of a Mixture of a Weak Acid (HA) and Salt of Its
Conjugate Base (MA) 294
4.20 Exact Treatment of a Mixture of a Weak Base (BOH) and Salt of Its
Conjugate Acid (BA) 297
4.21 Exact Treatment of a Mixture of a Strong Acid and a Weak Acid 299
4.22 Exact Treatment of a Mixture of Two Weak Acids 301
4.23 Buffer Solutions 306
4.24 Acid-Base Indicators 313
4.25 Titration of a Strong Monoprotic Acid with a Strong Base 319
4.26 Titration of a Weak Monoprotic Acid with a Strong Base 322
4.27 Titration of a Weak Base with a Strong Monoprotic Acid 325
4.28 General Treatment of Titration of an Acid with a Strong Base 329
4.29 Titration of a Dibasic Acid with a Strong Base 332
4.30 General Treatment of Titration of a Diprotic Acid with a Strong Base 339
4.31 Titration of Sodium Carbonate Solution with Hydrochloric Acid 341
4.32 Solubility Product 345
4.33 Equilibria Involving Complex Ions 361
4.34 Amphoterism 375
4.35 Some Concepts of Acids and Bases 378
4.36 Acid and Base Strengths and Structure 388

5. CoNDUCTANCE 406
5.1 Introduction 406
5.2 Metallic Conduction 406
5.3 Electrolytic Conduction 407
5.4 Electrolysis 408
5.5 Conductance of Solutions 410
5.6 Equivalent and Molar Conductivities 413
5.7 Variation of Conductivity and Molar Conductivity with Concentration 417
5.8 Conductivity at High Electric Fields and High Frequencies 423
5.9 Kohlrausch’s Law of Independent Migration of Ions 424
5.10 Values of Limiting Ionic Molar Conductivities 425
5.11 Transport Numbers 432
5.12 Ionic Speed and Ionic Mobility 455
5.13 The Walden’s Rule 459
5.14 Application of Conductance Measurements 460
Appendix I: A Note on Changing Concepts in Physical Chemistry 475
Appendix II: Units and Conversion Factors 501
Index 503
 1 Gaseous State

1.1 THE THREE STATES OF MATTER

Introduction In order to determine experimentally the properties of substances, we deal with
the aggregates of molecules as they occur in nature. It is the aggregations of
molecules which come within the scope of human experience that constitute
what is known as matter. The various kinds of substances that make up matter
can be divided roughly into three categories, namely, gases, liquids and solids.
These are called the three states of matter. These states can be considered to arise
as a result of competition between two opposing molecular forces, namely, the
forces of attraction which tend to hold the molecules together, and the disruptive
forces due to the thermal energy of molecules.
Gaseous State If the thermal energy is much greater than the forces of attraction, then we
have matter in its gaseous state. Molecules in the gaseous state move with very
large speeds and the forces of attraction amongst them are not sufficient to bind
the molecules at one place, with the result that the molecules move practically
independent of one another. Because of this feature, gases are characterized by
marked sensitivity of volume change with change in temperature and pressure.
There exists no boundary surface and, therefore, gases tend to fill completely
any available space, resulting in no fixed volume to the gaseous state.
Liquid State If the forces of attraction are greater than the thermal energy, we have matter
in the liquid state. Molecules in the liquid state too have kinetic energy but
they cannot go very far away because of the larger forces of attraction amongst
them. Due to this feature, liquids have definite volume, but no definite shape.
They take the shape of the vessel in which they are placed. In general, liquids
are more dense and less compressible than gases.
Solid State If the forces of attraction between molecules are much greater than the thermal
energy, the positions of the molecules remain fixed and we have matter in
the solid state. The molecules in the solid state, therefore, do not possess any
translational energy, but have only vibrational energy since they can vibrate
about their mean positions. Extremely large forces of attraction exist amongst
them. That is why solids differ markedly from liquids and gases in respect of
size, shape and volume. Solids, in general, have definite size, shape and volume.
Comments on the Of all the three states of molecular aggregation, only the gaseous state allows
Gaseous System a comparatively simple quantitative description. We are generally concerned
with the relations among four properties, namely, mass, pressure, volume and
2 A Textbook of Physical Chemistry

temperature. A system is in a definite state (or condition) when all the properties
of the system have definite values. It is not necessary to specify each and every
property of the matter as these are interrelated. The relationship which connects
the above four variables is known as the equation of state of the system. For
gases, only three of these must be specified to describe the state, the fourth
automatically has a fixed value and can be calculated from the equation of state
established from the experimental behaviour of the system.

1.2 EXPERIMENTALLY DERIVED GASEOUS LAWS

Boyle’s Law At constant temperature, the volume of a definite mass of a gas is inversely
proportional to its pressure, that is,
1 K
V μ i.e. V = or pV = K (1.2.1)
p p
where K is a constant whose value depends upon (i) nature of the gas, (ii)
temperature of the gas, and (iii) mass of the gas. For a given mass of a gas at
constant temperature, Boyle’s law gives
p1V1 = p2V2 (1.2.2)
where V1 and V2 are volumes at pressures p1 and p2, respectively.

Graphical Equation (1.2.1) can be represented graphically by plotting pressures as ordinates

Representation and the corresponding volumes as abscissae (Fig. 1.2.1). The nature of the curve
is a rectangular hyperbola. The general term isothermal or isotherm (meaning
at constant temperature) is used to describe these plots.

Fig. 1.2.1 A Typical

variation of pressure of a
gas with volume

Charles Law Charles made measurements of the volume of a fixed mass of a gas at various
temperatures under the condition of constant pressure and found that the
volume of a fixed mass of a gas at constant pressure is a linear function of
its Celsius temperature. This can be expressed as
Vt = a + bt (1.2.3)
where t is Celsius temperature and a and b are constants.
 Gaseous State 3

Graphical Equation (1.2.3) has been plotted in Fig. 1.2.2. The intercept on the vertical axis
Representation is a and it is equal to V0, the volume at 0 ºC. The slope of the plot is the
derivative
Ê ∂V ˆ
b= Á t˜
Ë ∂t ¯ p

Fig. 1.2.2 A typical

variation of volume of a
gas with temperature
expressed in ºC

Alternative Form of Experimental data shows that for each Celsius degree rise in temperature, the
Charles Law volume of a gas expands 1/273.15 of its volume at 0 ºC. If V0 is the volume
of a gas at 0 ºC, then b is given by

Ê V /273.15 ˆ
b= Á 0
Ë 1 ∞C ˜¯
With this, Eq. (1.2.3) becomes

Ê V /2.73.15 ˆ
Vt = V0 + Á 0 t
Ë 1 ∞C ˜¯

Ê t/ ∞ C ˆ Ê 273.15 + t/ ∞C ˆ
or Vt = V0 Á 1 + ˜ = V0 ÁË ˜ (1.2.4)
Ë 273.15 ¯ 273.15 ¯

or (T /K ) (T is kelvin temperature)†
VT = V0
273.15

†
It is convenient to use the absolute temperature scale on which temperatures are measured
in kelvin (K). A reading on this scale is obtained by adding 273.15 to the Celsius value.
Temperature on the kelvin scale is denoted by T. Thus

T/K = 273.15 + t/ ºC
4 A Textbook of Physical Chemistry

Ê V0 ˆ
i.e. VT = Á T
Ë 273.15 K ˜¯
Since V0, the volume of the gas at 0 ºC, has a constant value at a given
pressure, the above relation can be expressed as
V = K2T (1.2.5)
where K2 is a constant whose value depends upon the nature, mass and pressure
of the gas.
Equation (1.2.5) is an alternative form of Charles law according to which
the volume of a given mass of a gas at constant pressure is directly proportional
to its kelvin temperature.
Graphical A typical variation of volume of a gas with change in its kelvin temperature is
Representation shown in Fig. 1.2.3. The general term isobar, which means at constant pressure,
is assigned to these plots.

Fig. 1.2.3 Variation of

volume of a gas with
kelvin temperature

Comment on Zero Since volume is directly proportional to kelvin temperature, the volume of a gas
Kelvin should theoretically be zero at kelvin zero. However, gases liquefy and then
solidify before this low temperature is reached. In fact, no substance exists as
a gas at a temperature near kelvin zero, though the straight-line plots can be
extrapolated to zero volume. The temperature that corresponds to zero volume
is – 273.15 ºC.
Gay-Lussac’s Law: An expression similar to volume dependence of gas on temperature has been
Dependence of derived for the pressure dependence also. The pressure of a given mass of a gas
Pressure on at constant volume varies linearly with Celsius temperature.
Temperature
pt = a + bt (1.2.6)
where a = p0 and b = (∂pt /∂t)V. The value of the latter can be determined
 Gaseous State 5

experimentally and is found to be ( p0 /273.15 ºC). Thus, Eq. (1.2.6) modifies

to
Ê p0 ˆ
pt = p0 + Á (t / ∞C)
Ë 273.15 ˜¯

Ê 273.15 + (t / ∞C) ˆ Ê p0 ˆ
Therefore pt = p0 Á ˜¯ = Á ˜¯ T
Ë 273.15 Ë 273 .15 K

or pt μ T (1.2.7)
that is, the pressure of a given mass of a gas at constant volume is directly
proportional to its kelvin temperature.
Graphical Equations (1.2.6) and (1.2.7) are shown graphically in Figs. 1.2.4 and 1.2.5,
Representations respectively. The general term isochor (meaning at constant volume) is given to
the plots of Fig. 1.2.5.

Fig. 1.2.4 A typical

variation of pressure of
a gas with temperature
expressed in ºC

Fig. 1.2.5 A typical

variation of pressure of
a gas with kelvin
temperature

Graham’s Law of The phenomenon of diffusion may be described as the tendency for any substance
Diffusion to spread uniformly throughout the space available to it. Diffusion through fine
pores is called effusion.
According to Graham’s law of diffusion, the rate of diffusion (or effusion)
of a gas is inversely proportional to the square root of its density or molar mass.
If r1 and r2 are the rates of diffusion of two gases under identical conditions,
whose densities under the given conditions are ρ1 and ρ2, respectively, then
from Graham’s law,

r1 r2 r1 M2
= or = (1.2.8)
r2 r1 r2 M1
where M1 and M2 are the respective molar masses of the two gases.

1.3 EQUATION OF STATE

Derivation of The results of the laws of Boyle and Charles can be combined into an
Equation of State expression which represents the relationship between pressure, volume and
temperature of a given mass of a gas; such an expression is described as an
equation of state.
6 A Textbook of Physical Chemistry

Suppose the gas is in the initial state with volume V1, pressure p1 and
temperature T1. We then change the state of the gas to a volume V2, pressure
p2 and temperature T2. Let us carry out this change in two steps.
(i) First we change the pressure from p1 to p2 keeping the temperature T1
constant. The resultant volume Vr as given by Boyle’s law is
p1V1
Vr =
p2
(ii) Next, temperature is changed from T1 to T2, keeping the pressure p2
constant. The final volume V2 as given by Charles law is
V2 Vr Vr T2 ( p1V1 / p2 ) T2
= i.e. V2 = =
T2 T1 T1 T1

p1V1 p2V2
or = (1.3.1)
T1 T2
It follows that no matter how we change the state of the given amount of
a gas, the ratio pV/T always remains constant, i.e.

pV
=K
T
Universal Gas The value of K depends on the amount of gas in the system. Since V is an
Constant extensive property (which is mass dependent), its value at constant p and T is
proportional to the amount of the gas present in the system. Then K must also
be proportional to the amount of gas because p and T are intensive properties
(which have no mass dependence). We can express this by writing K = nR, in
which n is the amount of gas in a given volume of gas and R is independent
of all variables and is, therefore, a universal constant. We thus have the general
gas law
pV = nRT (1.3.2)
Physical The universal gas constant as given by Eq. (1.3.2) is R = pV/nT. Thus, it has the
units of (pressure × volume) divided by (amount of gas × temperature). Now the
Gas Constant R dimensions of pressure and volume are,
Pressure = (force/area) = (force/length2) = force × length–2
Volume = length3

Thus (force ¥ length -2 ) (length 3 ) (force ¥ length)

R= =
(amount of gas) (kelvin) (amount of gas) (kelvin)
work (or energy)
=
(amount of gas) (kelvin)
Thus, the dimensions of R are energy per mole per kelvin and hence it
represents the amount of work (or energy) that can be obtained from one mole
of a gas when its temperature is raised by one kelvin.
 Gaseous State 7

1.4 APPLICATION OF EQUATION OF STATE

Concept of an Ideal So far, we have assumed that all gases obey the gas laws under all conditions
Gas of temperature and pressure; however, for real gases this is not true. Real gases
obey these laws only under limited conditions of low pressures and high
temperatures. They exhibit deviations from the gaseous laws and these deviations
are greater when the temperature and pressure are close to the conditions at
which the gas can be condensed into a liquid. Thus Boyle’s law, Charles law,
and the equation of state derived from these two laws may be regarded as
approximations for real gases and are expected to be applicable only at relatively
low pressures and moderately high temperatures. It is, nevertheless, very useful
to postulate a hypothetical ideal gas, defined as a gas to which the laws of
Boyle and Charles are strictly applicable under all conditions of temperatures
and pressures. It is for this reason that Eq. (1.3.2) is commonly referred to as the
ideal gas equation. Real gases attain ideal behaviour only at very low pressures
and very high temperatures.
Characteristics of Since Eq. (1.3.2) is not applicable to real gases, the evaluation of the universal
an Ideal Gas gas constant R cannot be done directly by utilizing the pressure, volume, and
temperature data of real gases. Equation (1.3.2) is strictly applicable only for
ideal gases and thus if the pressure and volume of one mole of an ideal gas were
known at a definite temperature, it would be a simple matter to evaluate R from
Eq. (1.3.2). However, as no gas behaves ideally, this procedure would appear to
be ruled out. But we know from experiments that gases approach ideal behaviour
as the pressure is decreased. Hence, the extrapolation method ( p Æ 0) on the
data of real gases can be utilized to determine the corresponding properties of
an ideal gas. The data obtained in this manner, after extrapolation, should be
independent of the characteristics of the actual gas employed for the experiment.
By measuring the volumes of one mole of a real gas at different pressures
and constant temperature, a graph between pV and p can be drawn. On
extrapolating this graph to zero pressure to correct for departure from ideal
behaviour it is possible to determine the value of pV which is expected to be
applicable to one mole of an ideal gas. Since this value of pV is expected to
be independent of the nature of the gas, the same value of (pV)pÆ0 would be
obtained irrespective of the gas employed for this purpose. In other words, the
graphs of pV versus p of different gases must yield the same value of (pV)pÆ0.
In fact, it is found to be so, as is evident from Fig. 1.4.1. The value of (pV)pÆ0
at 273.15 K is found to be 22.711 dm3 bar. Thus if p = 1 bar, then V =
22.711 dm3, that is, the volume occupied by one mole of an ideal gas at standard
temperature (273.15 K) and pressure (1 bar) is 22.711 dm3.
Value of Gas The value of R in SI units can be worked out as follows.
Constant in SI Units

pV (1 bar) (22.711 dm3 )

R= = = 0.083 14 bar dm3 K -1 mol -1
nT (1 mol) (273.15 K)
Since 102 kPa = 1 bar, the value of R expressed in kPa dm3 K–1 mol–1 will be
8 A Textbook of Physical Chemistry

Fig. 1.4.1 Plots of pV

versus p of a few gases

R = 0.083 14 (102 kPa) dm3 K -1 mol -1

= 8.314 kPa dm 3 K -1 mol -1 ∫ 8.314 MPa cm 3 K -1 mol -1
∫ 8.314 Pa m 3 K -1 mol -1 ∫ 8.314 J K -1 mol -1

Example 1.4.1 Determine the value of gas constant R when pressure is expressed in Torr and volume
in dm3.
Solution By definition, 1.013 25 bar = 760 Torr. Hence
Ï Ê 760 Torr ˆ ¸ 3
Ì(1 bar) Á ˝ (22.711 dm )
pV Ó Ë 1.013 25 bar ˜¯ ˛
R= =
nT (1 mol) (273.15 K)
= 62.36 Torr dm 3 K -1 mol -1

Example 1.4.2 Derive the value of R when (a) pressure is expressed in atmospheres, volume in cm3 and
(b) p in dyn m–2 and V in mm3.
Solution Since pV = 22.711 dm3 bar, the volume of an ideal gas at 1 atm (= 1.013 25 bar) will be

22.711 dm 3 bar
V = = 22.414 dm 3
1.01325 bar
(a) p in atm and V in cm3

pV (1 atm) (22 414 cm 3 )

R= = = 82.06 atm cm 3 K -1 mol -1
nT (1 mol) (273.15 K)
(b) p in dyn m–2 and V in mm3

p = 1 atm ∫ 1.013 2 ¥ 106 dyn cm -2 ∫ 1.013 2 ¥ 1010 dyn m -2

V = 22 414 cm 3 ∫ 22 414 ¥ 103 mm 3
pV (1.013 2 ¥ 1010 dyn m -2 ) (22 414 ¥ 103 mm 3 )
R= =
nT (1 mol) (273.15 K)
= 8.314 ¥ 1014 (dyn m -2 ) (mm 3 ) K -1 mol -1
 Gaseous State 9

Avogadro’s Law According to Avogadro’s law, equal number of molecules of different gases under
identical conditions of temperature and pressure occupy the same volume.
When this law is applied to real gases, it is found that the law does not hold
good at ordinary temperatures and pressures. However, when the measurements
are made at low pressures, deviations from the law become less and thus, like
other gaseous laws, Avogadro’s law may be regarded as an approximation which
is expected to be applicable only under conditions of low pressures and high
temperatures. Strictly speaking, this law would be applicable only for ideal gases.
The fact that Avogadro’s law is applicable to real gases at very low pressures
and high temperatures indicates that the volume occupied by different gases
having the same number of molecules under identical conditions of temperature
and pressure is independent of the nature of the gaseous molecules. Thus,
whether the molecules are heavy (e.g. Br2) or light (e.g. H2), gases with equal
number of molecules would occupy the same volume. This leads to one of the
most important features of gases that the distance between molecules is much
larger than the actual dimensions of molecules, since otherwise, Avogadro’s law
would not have been true.
Avogadro Constant The facts that the behaviour of a real gas approaches that of an ideal gas as
p Æ 0 and the volume occupied by one mole of an ideal gas at the specified
temperature (273.15 K) and pressure (101.325 kPa) has a fixed value
(22.414 dm3) indicate that the number of molecules contained in one mole of
any real gas should be a constant quantity. This physical quantity has a value of
6.022 × 1023 mol–1 and is known as Avogadro constant.
Equation of State in The amount of gas containing N number of molecules is given by
Terms of Numbers
N
of Molecules n=
NA
With this, Eq. (1.3.2) becomes
N
pV = nRT = RT (1.4.1)
NA
Avogadro’s law follows directly from the Eq. (1.4.1). We have
Ê RT ˆ
V =Á N
Ë pN A ˜¯
For a fixed condition of pressure and temperature, a gas will have fixed
volume for a fixed number of gaseous molecules.

Example 1.4.3 Estimate the number of gaseous molecules left in a volume of 1 mm3 if it is pumped out
to give a vacuum of 10–6 mmHg at 298 K.
Solution We are given that

V = 1 mm 3 = 10 -6 dm 3
Ê 101.235 kPa ˆ
p = 10 -6 mmHg = (10 -6 mmHg) Á = 1.333 ¥ 10 -7 kPa
Ë 760 mmHg ¯˜
10 A Textbook of Physical Chemistry

pV (1.333 ¥ 10 -7 kPa) (10 -6 dm 3 )

Amount of the gas, n = =
RT (8.314 kPa dm 3 K -1 mol -1 ) (298 K )
= 5.38 ¥ 10 -17 mol
Hence, number of molecules
N = n NA = (5.38 ¥ 10–17 mol) (6.022 ¥ 1023 mol–1) = 3.240 ¥ 107

Equation of State in For a gas of mass m, the amount of gas is given by

Terms of Mass of a m
Gas n=
M
where M is the molar mass of the gas. With this, Eq. (1.3.2) becomes
Ê mˆ (1.4.2)
pV = nRT = Á ˜ RT
Ë M¯

Example 1.4.4 When 2 g of gaseous substance A is introduced into an initially evacuated flask kept
at 25 ºC, the pressure is found to be 101.325 kPa. The flask is evacuated and 3 g of B
is introduced. The pressure is found to be 50.662 5 kPa at 25 ºC. Calculate the ratio
MA/MB.
Solution From the ideal gas equation, we have

Ê mˆ RT
pV = nRT = Á ˜ RT or M =m
Ë M¯ pV

Hence RT RT
M A = (2 g) and M B = (3 g)
(101.325 kPa) V (50.662 5 kPa) V
MA 2 ¥ 0.5 1
Thus, = =
MB 3 3

Example 1.4.5 A certain mixture of helium and argon weighing 5.0 g occupies a volume of 10 dm3 at
25 ºC and 101.325 kPa. What is the composition of the mixture in mass percentage?
Solution Given that mmix = 5.0 g; V = 10 dm3; T = 25 ºC ∫ 298.15 K; p = 101.325 kPa
Let the mass of He be x. Therefore
m x
Amount of He = =
M (4.0 g mol -1 )
m 5.0 g - x
Amount of Ar = =
M (39.95 g mol -1 )
pV (101.325 kPa) (10 dm 3 )
Total amount of gases = =
RT (8.314 kPa dm 3 K -1 mol -1 ) (298.15 K)
= 0.409 mol

Ê x ˆ Ê 5.0 g - x ˆ
Hence + = 0.409 mol
ËÁ 4.0 g mol -1 ¯˜ ÁË 39.95 g mol -1 ¯˜
Solving for x, we get
x = 1.262 g
 Gaseous State 11

1.262 g
Mass per cent of He = ¥ 100 = 25.24
5.0 g
Mass per cent of Ar = 100 - 25.24 = 74.76

Example 1.4.6 A flask of 2 dm3 capacity contains O2 at 101.325 kPa and 300 K. The gas pressure is
reduced to 0.10 Pa by attaching the flask to a pump. Assuming ideal behaviour, answer
the following:
(i) What will be the volume of the gas which is left behind?
(ii) What amount of O2 and the corresponding number of molecules are left behind
in the flask?
(iii) If now 2 g of N2 is introduced, what will be the pressure of the flask?

Solution Given that V1 = 2 dm3, p1 = 101.325 kPa, p2 = 0.10 Pa, T = 300 K

We have the following results.
(i) The volume of O2 left behind will be the same, i.e. 2 dm3.
(ii) The amount of O2 left behind is given by
p2V1 (10 -4 kPa) (2 dm 3 )
n= = = 8.019 ¥ 10 -8 mol
RT (8.314 kPa dm 3 K -1 mol -1 ) (300 K)
N = nN A = (8.109 ¥ 10 -8 mol) (6.022 ¥ 1023 mol -1 )
= 4.88 ¥ 1016
1
(iii) 2 g of N2 = mol
14
1 1
Total amount of gases in flask = mol + 8.019 ¥ 10 -8 mol mol
14 14
Thus, the pressure of the flask is given by
nRT (1 mol/14) (8.314 kPa dm 3 K -1 mol -1 ) (300 K)
p= = = 89.08 kPa
V (2 dm 3 )

Example 1.4.7 Two flasks of equal volume connected by a narrow tube (of negligible volume) are at
300 K and contain 0.70 mol of H2 gas at 50.662 5 kPa pressure. One of the flasks is
then immersed into a bath kept at 400 K, while the other remains at 300 K. Calculate
the final pressure and the amount of H2 in each flask.
Solution The final pressure in both the flasks will be the same, since both of them are connected
with each other. Let n1 be the amount of the gas in flask 1 (T1 = 300 K) and n2 in the
flask 2 (T2 = 400 K);
For flask 1, pV = n1RT1 For flask 2, pV = n2RT2
n1 T2 400 K 4
Therefore, n1T1 = n2T2 i.e. = = =
n2 T1 300 K 3
But n1 + n2 = 0.7 mol
Hence n1 = 0.4 mol at 300 K n2 = 0.3 mol at 400 K
Volume of each flask is
nRT (0.35 mol) (8.314 kPa dm 3 K -1 mol -1 ) (300 K)
V = = = 17.23 dm 3
p (50.662 5 kPa)
12 A Textbook of Physical Chemistry

Final pressure is
n1RT1 (0.4 mol) (8.314 kPa dm 3 K -1 mol -1 ) (300 K)
pf = = = 57.90 kPa
V (17.23 dm 3 )

1.5 CONCEPTS OF PARTIAL PRESSURE AND PARTIAL VOLUME

The relation between the total pressure of a mixture of gases and the pressures
Pressure of the individual gases was expressed by Dalton in the forms of law of partial
pressures. The partial pressure of a gas in a mixture is defined as the pressure
which the gas would exert if it is allowed to occupy the whole volume of the
mixture at the same temperature.
According to Dalton’s law of partial pressures, the total pressure of a mixture
Law of gases is equal to the sum of the partial pressures of the constituent gases.
Partial Pressures in Let a mixture of gases have the amount n1 of the first gas, n2 of the second gas,
a Gaseous Mixture and so on. Let the corresponding partial pressures be p1, p2, The total pressure
is given by
ptotal = p1 + p2 +
If the gases present in the mixture behave ideally, then, it is possible to
write separately for each gas,

p1V = n1RT (1.5.1a)

p2V = n2RT (1.5.1b)
.....
Hence ( p1 + p2 + ) V = (n1 + n2 + ) RT
i.e. ptotal V = ntotal RT (1.5.2)
where ntotal is the total amount of gases in the mixture. Dividing Eqs (1.5.la)
and (1.5.1b) by Eq. (1.5.2), we get
n1
p1 = ptotal = x1 ptotal (1.5.3a)
ntotal
n2
p2 = ptotal = x2 ptotal (1.5.3b)
ntotal
The fractions n1/ntotal, n2/ntotal, are called the amount (mole) fractions of the
Amount (Mole) respective gases. The amount fraction of a constituent in any mixture (gaseous,
Fraction liquid or solid) is defined as the amount (or number of molecules) of that
constituent divided by the total amount (or number of molecules) of constituents
in the mixture. If xs are given, it is possible to calculate partial pressures by
using Eqs (1.5.3).
Partial Volumes: The partial volume of a gas in a mixture is defined as the volume which the gas
Amagat’s Law would occupy if it were present alone in a container at temperature T and
pressure p of the mixture. According to the ideal gas equation, this is given by
 Gaseous State 13

Ê RT ˆ
V1 = n1 Á (1.5.6a)
Ë p ˜¯

Ê RT ˆ
V2 = n2 Á (1.5.6b)
Ë p ˜¯

Adding, we get
RT Ê RT ˆ
V1 + V2 + ◊ ◊ ◊ = (n1 + n2 + ◊ ◊ ◊ ) = ntotal Á
P Ë p ˜¯
From the ideal gas equation

Ê RT ˆ
ntotal Á = Vtotal (1.5.7)
Ë p ˜¯

we have V1 + V2 + ◊ ◊ ◊ = Vtotal

which is Amagat’s law of partial volumes according to which the total volume of
a mixture of gases is equal to the sum of the partial volumes of the constituent
gases.
Dividing Eqs (1.5.6) by Eq. (1.5.7), we get
Vi = xi Vtotal i = 1, 2, . . . (1.5.8)

Example 1.5.1 The following reaction is carried out at 101.325 kPa and 383 K,
2CH4 + 3O2 Æ 2CO + 4H2O
with the initial amounts of CH4 and O2 as 0.01 mol and 0.03 mol, respectively. All reactants
and products are gaseous at 383 K. A short while after completion of the reaction, the
flask is cooled to 283 K at which temperature H2O is completely condensed. Calculate:
(i) The volume of the flask.
(ii) Total pressure and partial pressures of various species after the reaction at 383 K
and 283 K.
(iii) The number of molecules of the various substances before and after the reaction.
Solution The reaction is 2CH4 + 3O2 Æ 2CO + 4H2O
Amount/mol Temp.
In the beginning 0.01 0.03 0 0 383 K
At the end 0.0 0.015 0.01 0.02 383 K
0.0 0.015 0.01 condensed 283 K
(i) Volume of the flask

nRT (0.04 mol) (8.314 kPa dm 3 K -1 mol -1 ) (383 K)

V = = = 1.257 dm 3
p (101.325 kPa)
14 A Textbook of Physical Chemistry

Ê 0.045 mol ˆ
(ii) p(total, 383 K) = Á (101.325 kPa) = 113.99 kPa
Ë 0.040 mol ˜¯

Ê 0.025 mol ˆ Ê 283 K ˆ

p(total, 283 K) = Á (101.325 kPa) = 46.81 kPa
Ë 0.040 mol ˜¯ ÁË 383 K ˜¯

p(CH 4 , 383 K) = 0

Ê 0.015 mol ˆ
p(O2 , 383 K) = Á
Ë 0.045 mol ˜¯
(113.99 kPa) = 38.00 kPa

Ê 0.01 mol ˆ
p(CO, 383 K) = Á
Ë 0.045 mol ˜¯
(113.99 kPa) = 25.33 kPa

Ê 0.02 mol ˆ
p(H 2O, 383 K) = Á
Ë 0.045 mol ˜¯
(113.99 kPa) = 50.66 kPa

p(CH 4 , 283 K) = 0

Ê 0.015 mol ˆ
p(O2 , 283 K) = Á
Ë 0.025 mol ˜¯
(46.81 kPa) = 28.09 kPa

Ê 0.01 mol ˆ
p(CO, 283 K) = Á
Ë 0.025 mol ˜¯
(46.81 kPa) = 18.72 kPa

(iii) Number of molecules before the reaction are

N(CH4) = (0.01 mol) (6.022 × 1023 mol–1) = 6.022 × 1021
N(O2) = (0.03 mol) (6.022 × 1023 mol–1) = 1.807 × 1022
Number of molecules after the reaction are
N(CH4) = 0
N(O2) = (0.015 mol) (6.022 × 1023 mol–1) = 9.033 × 1021
N(CO) = (0.01 mol) (6.022 × 1023 mol–1) = 6.022 × 1021
N(H2O) = (0.02 mol) (6.022 × 1023 mol–1) = 1.204 × 1022

1.6 THE KINETIC GAS EQUATION

Postulates of an After knowing the experimental gas laws, it is of interest to develop a theoretical
Ideal Gas model based on the structure of gases, which can correlate the experimental
facts. Fortunately, such a theory has been developed (known as the kinetic
theory of gases) and based upon certain essential postulates (which are supposed
to be applicable to an ideal gas) it is possible to derive an expression (known
as the kinetic gas equation) from where all these gas laws can be derived. The
essential postulates are:
∑ A gas consists of a large number of very small spherical tiny particles,
which may be identified with the molecules. The molecules of a given gas
are completely identical in size, shape and mass.
 Gaseous State 15

∑ The volume occupied by the molecules is negligible in comparison to the

total volume of the gas.
∑ The molecules are in rapid motion which is completely random. During their
motion, they collide with one another and with the sides of the vessel. The
pressure of the gas is due to the collisions of molecules with the sides of the
vessel.
∑ The molecules are perfectly elastic, i.e. there occurs no loss of energy when
they collide with one another and with the sides of the vessel.
∑ The laws of classical mechanics, in particular Newton’s second law of motion,
are applicable to the molecules in motion.
∑ There is no force of attraction or repulsion amongst the molecules, i.e. they
are moving independent of one another.
∑ At any instant, a given molecule can have energy ranging from a small value
to a very large value, but the average kinetic energy remains constant for
a given temperature, i.e. the average kinetic energy is proportional to the
absolute temperature of the gas.
Derivation of the Imagine a cube of edge-length l, containing N molecules, each having a mass
Kinetic Gas of m. Molecules are moving at random in all directions, with speed covering a
Equation considerable range of values.
The velocity u of any molecule may be resolved into three-component
velocities designated as ux, uy and uz. These are in the three directions at right
angles to each other and parallel to the sides of the cube as shown in Fig. 1.6.1.
The component velocities are related by the expression
u2 = ux2 + uy2 + uz2 (1.6.1)

Considering the x-component motion of a molecule, we will have

Momentum of the molecule before collision with the side ABCD = mux.
Momentum of the molecule after collision with the side ABCD = – mux.

Fig. 1.6.1 Molecular

velocity and its
components
16 A Textbook of Physical Chemistry

Change of momentum of the molecule in a single collision with the side ABCD
= | 2mux |.
Since l is the edge length of the cube, the molecule has to travel a distance
2l to arrive back at the wall ABCD. The number of collisions per unit time with
the wall ABCD will be equal to ux /2l.
The total change of momentum per unit time due to such impacts is

Êu ˆ mux2
2 mux Á x ˜ =
Ë 2l ¯ l
According to Newton’s second law of motion
Force = mass ¥ acceleration
d(velocity) d
= mass ¥ = (mass ¥ velocity)
dt dt
d
= (momentum) = rate of change of momentum
dt
Hence, total force due to impacts of a single molecule with the wall ABCD of
the vessel is mux2 /l.
The area of the wall is l2. Hence, the pressure exerted due to the collision
of x-component velocity of a single molecule with the side ABCD is
mux2 /l mux2
px = = (1.6.2)
l2 V
where V is the volume of the vessel.
Since each molecule will exert similar pressure, the total pressure exerted
on the wall ABCD will be
N N
m
p= Â pix =
V
 uix2 (1.6.3)
i =1 i =1
Defining the mean square speed as
N
1
ux2 =
N
 uix2 (1.6.4)
i =1
we can write Eq. (1.6.3) as
mN 2 (1.6.5)
p= u
V x
Since the directions x, y and z are equivalent, we will also have

ux2 = uy2 = uz2 (1.6.6)

But from Eq. (1.6.1), we will have

u2 = ux2 + uy2 + uz2 (1.6.7)

 Gaseous State 17

From Eqs (1.6.6) and (1.6.7), we can write

1 2
ux2 = uy2 = uz2 = u (1.6.8)
3
Substituting this in Eq. (1.6.5), we get

mN Ê 1 2 ˆ 1
p= u mNu2
V ÁË 3 ˜¯
or pV = (1.6.9)
3

Example 1.6.1 Calculate the pressure exerted by 1023 gas particles each of mass 10–22 g in a container
of volume 1 dm3. The root mean square speed is 105 cm s–1.
Solution From the given data, we have
N = 1023; m = 10–22 g = 10–25 kg; V = 1 dm3 = 10–3 m3
5 –1 3 –1
u2 = 10 cm s = 10 m s
Therefore, from the kinetic gas equation

1 mNu2
p=
3 V

1 (10 –25 kg) (1023 ) (103 m s –1 )2

we have p=
3 (10 –3 m 3 )
1 1
= (107 ) kg m –1 s –2 = × 10 7 Pa
3 3

1.7 SOME DERIVATIONS FROM THE KINETIC GAS EQUATION

Kinetic Gas The kinetic gas equation (1.6.9) can be used to derive the various gaseous laws
Equation Involving and to define expressions for some useful quantities such as the root mean
Kelvin Temperature square speed and the average kinetic energy. Before deriving these, it is helpful
to write this equation in the following form:
One of the postulates of the kinetic theory of gases is

Average kinetic energy T

i.e. 1 2 1 2
mu μ T or mu = KT
2 2
where K is the proportionality constant. Introducing this in Eq. (1.6.9) we have

1 2 Ê1 ˆ 2
pV = mNu2 = N Á mu2 ˜ = NKT (1.7.1)
3 3 Ë2 ¯ 3
Now, we proceed to derive the various gaseous laws from Eq. (1.7.1).

Boyle’s Law The essential conditions for Boyle’s law to be applicable are:
18 A Textbook of Physical Chemistry

(i) Temperature (T) should remain constant.

(ii) Mass of the gas should remain constant. In other words, the total number
of molecules (N) remains unchanged.
Under these conditions, Eq. (1.7.1) yields

pV = constant or p 1
V
which is the expression for Boyle’s law.
Charles Law In this case:
(i) Pressure (p) remains fixed.
(ii) Mass of the gas remains unchanged, i.e. N is constant.
With these conditions, Eq. (1.7.1) yields
Ê 2 NK ˆ
V =Á T i.e. V = (constant) T or V T
Ë 3 p ˜¯
as required by Charles law.
Avogadro’s Law It states that under similar conditions of pressure and temperature, equal volume
of all gases contain equal number of molecules. Considering two gases, we have

2 2
p1V1 = N1 KT1 and p2V2 = N 2 KT2
3 3
Since p1 = p2 and T1 = T2, therefore

p1V1 (2 / 3) N1 KT1 V1 N1
= fi =
p2V2 (2 / 3) N 2 KT2 V2 N2

If volumes are identical, obviously N1 = N2.

Graham’s Law of The rate of diffusion or effusion can be assumed to be directly proportional to
Effusion the root mean square speed (or any other average speed). Thus

r1 u12
=
r2 u22

From Eq. (1.6.9), we have

3 pV
u2 =
mN
For 1 mol of an ideal gas
pV = RT
and N = NA (NA is Avogadro constant)
 Gaseous State 19

With these, the above equation becomes

3 RT 3 RT
u2 = = (1.7.2)
mN A M
where M is the molar mass of the gas.

r1 u12 3 RT/M1 M2
Thus, = = =
r2 u22 3 RT/M2 M1

which is Graham’s law of effusion.

Root Mean Square Root mean square (rms) speed is defined as the square root of the average of the
Speed squares of speeds, i.e.

u12 + u22 + ◊◊◊ + uN2

u2 =
N
According to Eq. (1.7.2), this is given as
3 RT
u2 = (1.7.3)
M
3 pVm
or u2 = (1.7.4)
M
Thus, rms speed is directly proportional to the square root of temperature and
inversely proportional to the square root of molar mass. Hence, at a given
temperature lighter molecules (say H2, He) move faster than the heavier molecules
(say O2, N2). There is no effect of change of pressure or volume on the rms
speed since, at a given temperature, pVm = constant.

Example 1.7.1 A bulb of capacity 1 dm3 contains 1.03 × 1023 gaseous hydrogen molecules and the
pressure exerted by these molecules is 101.325 kPa. Calculate the average square molecular
speed and the temperature.
Solution We have V = 1 dm3, N = 1.03 × 1023, p = 101.325 kPa

N 1.03 ¥ 1023
n= = = 0.171 mol
NA (6.022 ¥ 1023 mol -1 )
pV (101.325 kPa) (1 dm 3 )
T = = = 71.27 K
nR (0.171 mol) (8.314 kPa dm 3 K -1 mol -1 )
3RT 3(8.314 J K -1 mol -1 ) (71.27 K)
u2 = =
M (2.0 ¥ 10 -3 kg mol -1 )
= 8.888 ¥ 105 J kg -1 ∫ 8.888 ¥ 105 (m s -1 )2

Average Kinetic The average kinetic energy (KE) is defined as

Energy
1 2
KE = mu
2
20 A Textbook of Physical Chemistry

According to Eq. (1.7.1), this is given as

3 pV
KE =
2 N
For 1 mole of an ideal gas
pV = RT and N = NA
With these, the above equation becomes
3 RT 3
KE = = kT (1.7.5)
2 NA 2
where k = R/NA and is known as the Boltzmann constant. Its value is given by

R 8.314 J K -1 mol -1
k= = = 1.380 6 ¥ 10 -23 J K -1
NA 6.022 ¥ 1023 mol -1
The total kinetic energy for 1 mole of the gas is
3 (1.7.6)
Etotal = N A (KE) = RT
2

Example 1.7.2 For a gas containing 1023 molecules (each having mass 10–22 g) in a volume of
1 dm3, calculate the total kinetic energy of molecules if their root mean square speed is
105 cm s–1. What will be its temperature?
Solution Total kinetic energy
Ê1 ˆ Ï1 ¸
= N Á mu2 ˜ = (1023 ) Ì (10 –25 kg) (103 m s –1 )2 ˝
Ë2 ¯ Ó2 ˛
= 0.5 ¥ 10 4 kg m 2 s –2 = 0.5 × 10 4 J
Total kinetic energy is also equal to N(3/2) kT. Thus
Ê 3ˆ
N Á ˜ kT = 0.5 ¥ 10 4 J
Ë 2¯

Hence 2 (0.5 ¥ 10 4 J) 2 (0.5 ¥ 10 4 J)

T = =
3 Nk 3 (1023 ) (1.380 6 ¥ 10 -23 J K -1 )
= 2 414 K

Example 1.7.3 Calculate the total kinetic energy of 0.5 mol of an ideal gas at 273 K.

Solution Total Kinetic energy

Ê3 ˆ Ï3 ¸
= n Á RT ˜ = (0.5 mol) Ì (8.314 J K -1 mol -1 ) (273 K)˝ = 1 702 J
Ë2 ¯ Ó2 ˛

1.8 REAL GASES

Deviation from Ideal Real gases do not obey the ideal gas laws exactly under all conditions of
Behaviour temperature and pressure. Experiments show that at low pressure and moderately
 Gaseous State 21

high temperatures, gases obey the laws of Boyle, Charles and Avogadro
approximately, but as the pressure is increased or the temperature is decreased,
a marked departure from ideal behaviour is observed. Figure 1.8.1 shows,
for example, the type of deviation that occurs in Boyle’s law for H2 at room
temperature.
Ideal gas

Fig. 1.8.1 Plot of p

versus V of hydrogen,
as compared to that
of an ideal gas
The curve for the real gas has a tendency to coincide with that of an ideal
gas at low pressures when the volume is large. At higher pressures, however,
deviations are observed.
Compression The deviations can be displayed more clearly, by plotting the ratio of the
Factor observed molar volume Vm to the ideal molar volume Vm, ideal (= RT/p) as a
function of pressure at constant temperature. This ratio is called the compression
factor Z and can be expressed as
Vm p
Z= = V (1.8.1)
Vm,ideal RT m

Example 1.8.1 At 273.15 K and under a pressure of 10.132 5 MPa, the compression factor of O2 is
0.927. Calculate the mass of O2 necessary to fill a gas cylinder of 100 dm3 capacity
under the given conditions.
Solution From the given data, we have
T = 273.15 K, Z = 0.927, p = 10.132 5 MPa
Thus, the molar volume of O2 is
ZRT (0.927) (8.314 MPa cm 3 K -1 mol -1 ) (273.15 K)
Vm = =
p 10.132 5 MPa
= 207.77 cm 3 mol -1
The mass of this molar volume will be equal to the molar mass of oxygen, i.e.
207.77 cm3 weighs 0.032 kg. Thus, the mass of oxygen required to fill a gas cylinder of
100 dm3 (i.e. 105 cm3) under the given condition is
Ê 0.032 kg ˆ 5 3
Á ˜ (10 cm ) = 15.40 kg
Ë 207.77 cm 3 ¯
22 A Textbook of Physical Chemistry

Example 1.8.2 The compression factor (Z = pV/nRT) for N2 at 223 K and 81.06 MPa is 1.95 and at
373 K and 20.265 MPa it is 1.10. A certain mass of N2 occupies a volume of 1.0 dm3
at 223 K and 81.06 MPa. Calculate the amount of the gas and the volume occupied by
the same quantity of N2 at 373 K and 20.265 MPa.

Solution For T = 223 K, p = 81.06 MPa, Z = 1.95 and V = 1.0 dm3 = 103 cm3, we have

pV (81.06 MPa) (103 cm 3 )

n= = = 22.42 mol
ZRT (1.95) (8.314 MPa cm 3 K -1 mol -1 ) (223 K)

Now at T = 373 K, p = 20.265 MPa, Z = 1.10, the volume occupied would be

Z n RT (1.10) (22.42 mol) (8.314 MPa cm 3 K –1 mol –1 ) (373 K)

V = =
p (20.265 MPa)
= 3 774.0 cm 3 = 3.774 dm 3

Plots of For an ideal gas, Z = 1 and is independent of pressure and temperature. For a
Compression real gas, Z = f (T, p), a function of both temperature and pressure. Figure 1.8.2
Factor versus shows a graph between Z and p for some gases at 273.15 K, the pressure range
Pressure in this graph is very large. It can be noted that:
(1) Z is always greater than 1 for H2.
(2) For N2, Z < 1 in the lower pressure range and is greater than 1 at higher
pressures. It decreases with increase of pressure in the lower pressure region,
passes through a minimum at some pressure and then increases continuously
with pressure in the higher pressure region.
(3) For CO2, there is a large dip in the beginning. In fact, for gases which are
easily liquefied, Z dips sharply below the ideal line in the low pressure region.

Fig. 1.8.2 Plots of Z

versus p of a few gases
 Gaseous State 23

Figure 1.8.2 gives an impression that the nature of deviations depend

upon the nature of the gas. In fact, it is not so. The determining factor is the
temperature relative to the critical temperature (see p. 36) of the particular gas;
near the critical temperature, the pV curves are like those for CO2, but when
far away, the curves are like those for H2 (Fig. 1.8.3).

Fig. 1.8.3 Plots of Z

versus p of a single gas at
various temperatures

Provided the pressure is of the order of 1 bar or less, and the temperature
is not too near the point of liquefaction, the observed deviations from the ideal
gas laws are not more than a few per cent. Under these conditions, therefore,
the equation pV = nRT and related expressions may be used.

1.9 VAN DER WAALS EQUATION OF STATE FOR A REAL GAS

Causes of Deviations The ideal gas laws can be derived from the kinetic theory of gases which is
from Ideal Behaviour based on the following two important assumptions:
(i) The volume occupied by the molecules is negligible in comparison to the
total volume of the gas.
(ii) The molecules exert no forces of attraction upon one another.
It is because neither of these assumptions can be regarded as applicable
to real gases that the latter show departure from the ideal behaviour.
Evidence for The molecules of a gas, however, do occupy a certain volume as can be seen
Molecular Volume from the fact that gases can be liquefied and solidified at low temperatures and
high pressures. On decreasing the temperature of a gas, the thermal energy
of molecules is decreased and the effect of applying high pressure is to bring
the molecules closer to one another, thereby increasing the forces of attraction
amongst them. Both these factors favour liquefaction and solidification. In the
solid state, however, there is a considerable resistance to any further attempt at
compression. It is, therefore, apparent that the molecules of a gas must have an
appreciable volume, which is probably of the same order as that occupied by
the same number of molecules in the solid state.
24 A Textbook of Physical Chemistry

Evidence for The molecules in gases also have weak forces of attraction (called van der Waals
Molecular attraction) amongst themselves, as otherwise, the gases could never be liquefied
Attractions and solidified. This is also supported by the fact that when a compressed gas
is passed through a porous plug of silk or cotton in adiabatic condition, the
emerging gas is found to be cooler than the entering gas provided the temperature
of the gas is less than its inversion temperature (Joule-Thomson effect).† This
is because on expansion, some work has to be done against the internal forces
of attraction, which requires energy. This energy comes from the system itself.
Derivation of Van Van der Waals was the first to introduce systematically the correction terms due
der Waals Equation to the above two invalid assumptions in the ideal gas equation piVi = nRT. His
corrections are given below.
Correction for Vi in the ideal gas equation represents an ideal volume where the molecules can
Volume move freely. In real gases, a part of the total volume is, however, occupied by
the molecules of the gas. Hence, the free volume Vi is the total volume V minus
the volume occupied by the molecules. If b represents the effective volume
occupied by the molecules of 1 mole of a gas, then for the amount n of the
gas Vi is given by

Vi = V – nb (1.9.1)
where b is called the excluded volume or co-volume. The numerical value of
b is four times the actual volume occupied by the gas molecules. This can be
shown as follows.
Expression of If we consider only bimolecular collisions, then the volume occupied by the
Excluded sphere of radius 2r represents the excluded volume per pair of molecules as
Volume shown in Fig. 1.9.1.

Fig. 1.9.1 Excluded

volume per pair of
molecules

Thus, excluded volume per pair of molecules

4 Ê4 ˆ
= p(2r )3 = 8 Á pr 3 ˜
3 Ë3 ¯

†
See Section 2.9 of Volume 2 of this series of book
 Gaseous State 25

Excluded volume per molecule

1 È Ê 4 3ˆ ˘ Ê4 ˆ
= 8 Á pr ˜ ˙ = 4 Á pr 3 ˜ = 4 (volume occupied by a molecule)
2 ÍÎ Ë 3 ¯˚ Ë3 ¯
Since b represents excluded volume per mole of the gas, it is obvious that
È Ê4 ˆ˘
b = N A Í 4 Á pr 3 ˜ ˙ (1.9.2)
Î 3 Ë ¯˚
Correction for Consider a molecule A in the bulk of a vessel as shown in Fig. 1.9.2. This
Forces of Attraction molecule is surrounded by other molecules in a symmetrical manner, with the
result that this molecule on the whole experiences no net force of attraction.

Fig. 1.9.2 Arrangement

of molecules within and
near the surface of a
vessel

Now, consider a molecule B near the side of the vessel, which is about to strike
one of its sides, thus contributing towards the total pressure of the gas. There
are molecules only on one side of the vessel, i.e. towards its centre, with the
result that this molecule experiences a net force of attraction towards the centre
of the vessel. This results in decreasing the velocity of the molecule, and hence
its momentum. Thus, the molecule does not contribute as much force as it would
have, had there been no forces of attraction. Thus, the pressure of a real gas
would be smaller than the corresponding pressure of an ideal gas, i.e.
pi = p + correction term (1.9.3)
This correction term depends upon two factors:
(i) The number of molecules per unit volume of the vessel Larger the
number, larger the net force of attraction with which the molecule B is dragged
behind. This results in a greater decrease in the velocity of the molecule B and
hence a greater decrease in the rate of change of momentum. Consequently, the
correction term also has a large value. If n is the amount of the gas present in
the volume V of the container, the number of molecules per unit volume of the
container is given as
nN A or n
N¢ = N¢ μ
V V
Thus, the correction term is given as:

Correction term n (1.9.4a)

V
26 A Textbook of Physical Chemistry

(ii) The number of molecules striking the side of the vessel per unit time
Larger this number, larger the decrease in the rate of change of momentum.
Consequently, the correction term also has a larger value. Now, the number
of molecules striking the side of vessel in a unit time also depends upon the
number of molecules present in unit volume of the container, and hence in the
present case:
n
Correction term (1.9.4b)
V
Taking both these factors together, we have

Correction term Ê nˆ Ê nˆ
ÁË V ˜¯ ÁË V ˜¯
2
or Correction term = a n (1.9.5)
V2
where a is the proportionality constant and is a measure of the forces of attraction
between the molecules. Thus
2
pi = p + a n (1.9.6)
V2
The unit of the term an2/V 2 is the same as that of the pressure. Thus,
the SI unit of a is Pa m6 mol–2. It may be conveniently expressed in kPa dm6
mol–2.
Expression of When the expressions as given by Eqs (1.9.1) and (1.9.6) are substituted in the
Van der Waals ideal gas equation piVi = nRT, we get
Equation of State
Ê n2 a ˆ
Á p + 2 ˜ (V - nb) = nRT
(1.9.7)
Ë V ¯
This equation is applicable to real gases and is known as the van der Waals
equation.
Values of Van der The constants a and b in van der Waals equation are called van der Waals
Waals Constants constants and their values depend upon the nature of the gas (Table 1.9.1). They
Table 1.9.1 Van der Waals Constants
a b a b
Gas Gas
6 –2 3 –1 6 –2
kPa dm mol dm mol kPa dm mol dm mol–1
3

H2 21.764 0.026 61 CH4 228.285 0.042 78

He 3.457 0.023 70 C2H6 556.173 0.063 80
N2 140.842 0.039 13 C3H8 877.880 0.084 45
O2 137.802 0.031 83 C4H10(n) 1 466.173 0.122 6
Cl2 657.903 0.056 22 C4H10(iso) 1 304.053 0.114 2
NO 135.776 0.027 89 C5H12(n) 1 926.188 0.146 0
NO2 535.401 0.044 24 CO 150.468 0.039 85
H2O 553.639 0.030 49 CO2 363.959 0.042 67
 Gaseous State 27

are characteristics of the gas. The values of these constants are determined by
the critical constants of the gas. Actually, the so-called constants vary to some
extent with temperature and this shows that the van der Waals equation is not
a complete solution of the behaviour of real gases.

Example 1.9.1 Calculate the pressure exerted by 22 g of carbon dioxide in 0.5 dm3 at 298.15 K using:
(a) the ideal gas law and (b) van der Waals equation. Given:
a = 363.76 kPa dm6 mol–2 and b = 42.67 cm3 mol–1
22 g
Solution Amount of CO2 = = 0.5 mol
44 g mol 1
V = 0.5 dm3 T = 298.15 K
a = 363.76 kPa dm6 mol–2 b = 42.67 cm3 mol–1 = 0.042 67 dm3 mol–1
(a) From the ideal gas law, p = nRT/V, we have
(0.5 mol) (8.314 kPa dm 3 K -1 mol -1 ) (298.15 K)
p= = 2.479 ¥ 103 kPa
(0.5 dm 3 )

(b) From the van der Waals equation, p = nRT n2 a

– 2 , we have
V – nb V
(0.5 mol) (8.314 kPa dm 3 K -1 mol -1 ) (298.15 K)
p=
0.5 dm 3 - (0.5 mol) (0.042 67 dm 3 mol -1 )

(0.5 mol)2 (363.76 kPa dm 6 mol -2 )

–
(0.5 dm 3 )2
p = 2 589.31 kPa – 363.76 kPa = 2 225.55 kPa

Example 1.9.2 Two van der Waals gases have the same value of b but different a values. Which of these
would occupy greater volume under identical conditions? If the gases have the same a
value but different values of b which would be more compressible?
Solution If two gases have same value of b but different values of a, then the gas having a larger
value a will occupy lesser volume. This is because the gas with a larger value of a will
have a larger force of attraction, and hence lesser distance between its molecules.
If two gases have the same value of a but different values of b, then the smaller the
value of b, larger will be the compressibility because the gas with the smaller value of
b will occupy lesser volume and hence will be more compressible.

Example 1.9.3 Calculate molecular diameter d of helium from its van der Waals constant b
(b = 24 cm3 mol–1).
Solution Since b = 4 × volume occupied by the molecules in 1 mole of a gas

or b = 4 N ÊÁ 4 pr 3 ˆ˜
AË ¯
3
1/3 1/3
Ê 3b ˆ ÔÏ 3 ¥ 24 cm 3 mol -1 ¸Ô
therefore r= Á ˜ = Ì -1 ˝
Ë 16N A p ¯ ÔÓ16(6.022 ¥ 10 mol ) (3.14) Ô˛
23

= 1.335 × 10–8 cm = 133.5 pm

d = 2r = 267 pm
28 A Textbook of Physical Chemistry

Example 1.9.4 The molar volume of helium at 10.132 5 MPa and 273 K is 0.011 075 of its molar
volume at 101.325 kPa at 273 K. Calculate the radius of helium atom. The value of a
may be neglected.
Solution The van der Waals equation after neglecting a reduces to
p(Vm – b) = RT
Substituting the given data, we have
at 101.325 kPa:
(101.325 kPa) (Vm – b) = (8.314 kPa dm3 K–1 mol–1) (273 K)
i.e. Vm – b = 22.4 dm3 mol–1 = 22.4 × 103 cm3 mol–1 (1)
at 10.132 5 MPa:
(10.132 5 MPa) (0.011 075 Vm – b) = (8.314 MPa cm3 K–1 mol–1) (273 K)
i.e. 0.011 075 Vm – b = 224.00 cm3 mol–1 (2)
Multiplying Eq. (1) by 0.011 075 and then subtracting Eq. (2) from it, we get
b – 0.011 075 b = (248.08 – 224) cm3 mol–1
24.08 cm 3 mol -1
b= = 24.35 cm 3 mol -1
0.988 925

Ê4 ˆ
Since b = Á pr 3 ˜ (4 N A )
Ë3 ¯
1/3 1/3
Ê 3b ˆ Ê 3 ¥ 24.35 cm 3 mol -1 ˆ
we have r=Á ˜ =Á -1 ˜
Ë 16pN A ¯ Ë 16 ¥ 3.14 ¥ 6.022 ¥ 10 mol ¯
23

= 1.34 ¥ 10 -8 cm = 134 pm

Applicability of the Since the van der Waals equation is applicable to real gases, it is worth
van der Waals considering how far this equation can explain the experimental behaviour of
Equation real gases, as represented by Fig. 1.8.2. The van der Waals equation for 1 mole
of a gas is
Ê a ˆ
Á p + 2 ˜ (Vm - b) = RT (1.9.8)
Ë Vm ¯

At low pressure When pressure is low, the volume is sufficiently large and b
can be ignored in comparison to Vm in Eq. (1.9.8). Thus, we have
Ê a ˆ a
Á p + 2 ˜ Vm = RT or pVm + = RT
Ë Vm ¯ Vm

a
or Z=1– (1.9.9)
Vm RT
From the above equation it is clear that in the low pressure region, Z is
less than 1. On increasing the pressure in this region, the value of the term
 Gaseous State 29

(a/VmRT) increases as V is inversely proportional to p. Consequently, Z

decreases with increase of p.

At high pressure When p is large, Vm will be small and one cannot ignore b
in comparison to Vm. However, the term a/Vm2 may be considered negligible in
comparison to p in Eq. (1.9.8). Thus,

p(Vm – b) = RT

or Z = 1 + pb (1.9.10)
RT
Here Z is greater than 1 and it increases linearly with pressure. This
explains the nature of the graph in the high pressure region.

At high temperature and low pressure If temperature is high, Vm will also

be sufficiently large and thus the term a/Vm2 will be negligibly small. At this
stage, b may also be negligible in comparison to Vm. Under these conditions,
Eq. (1.9.8) reduces to an ideal gas equation of state:

pVm = RT
Hydrogen and helium The value of a is extremely small for these gases as they
are difficult to liquefy. Thus, we have the equation of state as p(Vm – b) = RT,
2
obtained from the van der Waals equation by ignoring the term a/V m . Hence,
Z is always greater than 1 and it increases with increase of p.
The van der Waals equation is a distinct improvement over the ideal gas
law. It gives qualitative reasons for the deviations from ideal behaviour. However,
the generality of the equation is lost as it contains two constants, the values of
which depend upon the nature of the gas.

1.10 OTHER EQUATIONS OF STATE FOR REAL GASES

Berthelot’s Equation The van der Waals equation is one of the many equations of state suggested
in order to account for the behaviour of real gases. There are two other simple
equations of state which involve just two arbitrary constants. The first of these,
due to Berthelot, is

Ê n2 a ˆ
Á p + ˜ (V - nb) = nRT (1.10.1)
Ë TV 2 ¯
where a and b are constants called the Berthelot’s constants (different from van
der Waals constants) and are characteristics of the gas.

Dieterici’s Equation The second equation, due to Dieterici, is

{p exp(na/VRT )} (V – nb) = nRT (1.10.2)

30 A Textbook of Physical Chemistry

Virial Equation All these three equations of state can be expressed approximately in one common
form, called the virial equation of state, which has the following form for 1 mole
of a gas

pVm 1 1 1
Z= =1+B + C 2 + D 3 + ◊◊◊ (1.10.3)
RT Vm Vm Vm
where B, C, . . . are temperature dependent constants known as second, third,
etc., virial coefficients. These coefficients must be evaluated experimentally at
each different temperature.
The second virial coefficient B may be obtained from the experimental
data. Rearranging the virial equation, we get

Ê pV ˆ C
Vm Á m - 1˜ = B + + ◊◊◊
Ë RT ¯ Vm
Thus, extrapolating the graph between Vm{(pVm/RT) – 1} versus l/Vm to
l/Vm = 0 gives the value of B, i.e.

È pV ˘
B = lim Vm Í m - 1˙ (1.10.4)
Vm Æ• Î RT ˚
The third virial coefficient C would be the slope of this plot if there were
no higher terms in Eq. (1.10.3). These further terms cause the plot to be curved
so that C must be evaluated from the initial slope.
Physical The second virial coefficient B has the unit of volume and may be considered
Significance of to be an excluded molar volume as can be shown by using statistical mechanics.
the Constant B The term B can be expressed in terms of intermolecular attraction by the equation

•
B = 2 pN A Ú0 {1 - exp (-Φ /kT )}r
2 (1.10.5)
dr

where r is the intermolecular distance, k is the Boltzmann constant and Φ is the

potential of molecular interaction. As the simplest example of the use of this
equation, we consider a gas made up of rigid spherical molecules of diameter
d. We assume that the molecules do not interact unless they touch one another
and thus Φ = 0 if r > d. The molecules cannot penetrate one another as they
are rigid; thus Φ = • if r < d. Therefore, we have

d 2 2 Ê4 ˆ
B = 2pN A Ú0 r dr = pN d 3 = 4N A Á pr 3 ˜
3 A Ë3 ¯
(1.10.6)

Hence B is the product of Avogadro constant and the volume excluded per
molecule.
In general, the numerical values of the virial coefficients decrease very
sharply with higher powers of volume.
 Gaseous State 31

Problem 1.10.1 Show that at low densities, the van der Waals equation
Ê aˆ
Á p + 2 ˜ (Vm - b) = RT
Ë Vm ¯
and the Dieterici’s equation
p(Vm – b) = RT exp( – a/RTVm)

give essentially the same value of p.

Solution At low densities, volume of the gas is large, therefore b may be ignored in comparison to
Vm. Moreover, the term a/RTVm will have small value and thus the term exp( – a/RTVm)
can be expanded as
a
exp( – a/RTVm) 1–
RTVm
Thus, under these approximations we can write van der Waals equation as
Ê aˆ RT a
Á p + 2 ˜ (Vm ) = RT or p= -
Ë Vm ¯ Vm Vm2

and Dieterici’s equation as

RT Ê a ˆ RT a
p= Á 1 - RTV ˜ = V - 2
Vm Ë m¯ m Vm

Thus, we see that both van der Waals equation and Dieterici’s equation reduce to the
same expression of p at low densities.

1.11 REDUCTION OF VAN DER WAALS EQUATION TO VIRIAL EQUATION

Virial Equation in The van der Waals equation of state for 1 mole of a gas is
Volume
Ê a ˆ RT a
Á p + 2 ˜ (Vm - b) = RT or p= - 2
Ë Vm ¯ Vm - b Vm

Multiplying both sides by Vm/RT, we get

-1
pVm Vm a Ê b ˆ a
= - Z = Á1 - -
Vm ˜¯
or
RT Vm - b Vm RT Ë Vm RT

In the low pressure region, Vm is large and b/Vm << 1. Thus, the expression
(1 – b/Vm)–1 can be expanded into a power series in b/Vm:
-1 2 3
Ê b ˆ b Ê b ˆ Ê b ˆ
Á1 - V ˜ =1+ +Á ˜ + Á ˜ + ◊◊◊
Ë m¯ Vm Ë Vm ¯ Ë Vm ¯
32 A Textbook of Physical Chemistry

Substituting this in the expression for Z, we get

2
Ê a ˆ 1 Ê b ˆ
Z = 1 + Áb - + Á ˜ + ◊◊◊ (1.11.1)
Ë ˜
RT ¯ Vm Ë Vm ¯
Thus for the second virial coefficient, we have
a
B=b-
RT
Third virial coefficient C = b2, and so on.
Virial Equation in An alternative form of the virial equation of state involves the expression of
Pressure Z in terms of a power series in p, i.e.
Z = 1 + A1 p + A2p2 + (1.11.2)
The expressions for A1 and A2 can be derived as follows:
2
Ê a ˆ 1 Ê b ˆ
Z = 1 + Áb - ˜ + Á ˜ + ◊◊◊
Ë RT ¯ Vm Ë Vm ¯
Since Z = pVm /RT, therefore, 1/Vm = p/RTZ. Hence
2
Ê a ˆ p Ê p ˆ (1.11.3)
Z = 1 + Áb - ˜ + b2 Á + ◊◊◊
Ë ¯
RT RTZ Ë RTZ ˜¯
Comparing Eqs (1.11.2) and (1.11.3), we get
2
Ê a ˆ p Ê b ˆ 2
1 + A1 p + A2 p2 + ◊ ◊ ◊ = 1 + Á b - +Á p + ◊◊◊
Ë RT ˜¯ RTZ Ë RTZ ˜¯
22
1 Ê a ˆ Ê b ˆ p
or A1 p + A2 p2 + ◊ ◊ ◊ = b - p + ÁË RT ˜¯ 2 + ◊ ◊ ◊
RTZ ÁË RT ˜¯ Z
Dividing by p, we get
2
1 Ê a ˆ Ê b ˆ p
A1 + A2 p + ◊ ◊ ◊ = Á b- + + ◊◊◊
RTZ Ë RT ˜¯ ÁË RT ˜¯ Z 2
In the limiting state of zero pressure, Z = 1 and this equation becomes

1 Ê a ˆ
A1 =
RT ÁË b - RT ˜¯ (1.11.4)

which is the required expression for A1. Thus

2
Ê 1ˆ Ê b ˆ p
A1 + A2 p + ◊ ◊ ◊ = A1 Á ˜ + Á + ◊◊◊
Ë Z ¯ Ë RT ˜¯ Z 2
We repeat the procedure by subtracting A1 from both sides of this equation,
dividing by p and taking the limiting value at zero pressure. Note that
(Z – 1)/p = A1 at zero pressure. Then
 Gaseous State 33

2
Ê b ˆ a Ê a ˆ
A2 = Á ˜ - A12 = Á 2b - (1.11.5)
Ë RT ¯ ( RT ) Ë
3 RT ˜¯
Thus, the expression for Z correct up to the third coefficient is

1 Ê a ˆ a Ê a ˆ 2
Z =1+ ÁË b - RT ˜¯ p + 3 Á
2b -
RT ˜¯
p + ◊◊◊ (1.11.6)
RT ( RT ) Ë
The correct coefficient for p could have been obtained by simply replacing
l/Vm in Eq. (1.11.1) by the ideal value; however, this would yield incorrect values
of the coefficients of higher powers of pressures.
The slope of Z versus p curve is obtained by differentiating the above virial
equation in Z with respect to pressure, keeping the temperature constant, i.e.
Ê ∂Z ˆ 1 Ê a ˆ 2a Ê a ˆ
ÁË ∂p ˜¯ = RT ÁË b - RT ˜¯ + 3 Á
2b -
RT ˜¯
p + ◊◊◊ (1.11.7)
T ( RT ) Ë
At p = 0, all higher terms drop out and this derivative simply reduces to

Ê ∂Z ˆ 1 Ê a ˆ
ÁË ∂p ˜¯ = RT ÁË b - RT ˜¯ ; ( p = 0) (1.11.8)
T

Comment on the The derivative in Eq. (1.11.8) is the initial slope of the plot of Z versus p
Plots of (Fig. 1.8.2). Now if b > a/RT, the initial slope is positive and the size effect
Compression (i.e. b factor) will dominate the behaviour of the gas. However, if b < a/RT, the
Factor versus initial slope is negative and the effect of the attractive forces (i.e. a factor) will
Pressure dominate. Thus, the van der Waals equation, which includes both the effects of
size and of intermolecular forces, can interpret both the positive and negative
slopes of the Z versus p plots. In interpreting Fig. 1.8.2, we can say that at
0 °C, the effect of attractive forces dominate the behaviour of methane and
carbon dioxide, while the molecular size effect dominates the behaviour of
hydrogen.
While interpreting Fig. 1.8.3 (graph of Z versus p of the same gas at
different temperatures), we can say that if the temperature is low enough, the
term a/RT will be larger than b and so the initial slope of Z versus p will be
negative. As the temperature rises, a/RT becomes smaller. At a sufficiently
high temperature it becomes less than b, and the initial slope of Z versus p
curve turns positive.
Boyle Temperature At some intermediate temperature TB, called Boyle temperature, the initial slope
is zero. This is obtained from Eq. (1.11.8) by putting b – a/RTB = 0, which
yields
a (1.11.9)
TB =
Rb
At the Boyle temperature, the Z versus p line of an ideal gas is tangent
to that of a real gas when p approaches zero. The latter rises above the ideal
gas line only very slowly. In Eq. (1.11.6) the second term is zero at TB and the
34 A Textbook of Physical Chemistry

remaining terms are small until the pressure becomes very high. Thus, at the
Boyle temperature, the real gas behaves ideally over a wide range of pressure,
because the effects of the size of molecules and intermolecular forces roughly
compensate each other.
The Boyle temperature of some gases are given below:
TB(H2) = – 156 ºC TB(N2) = 59 ºC
TB(He) = – 249 ºC TB(CH4) = 224 ºC
TB(NH3) = 587 ºC
Thus we can see that for H2 and He, the temperature of 0 °C is above their
respective Boyle temperatures and so they have Z values greater than unity. The
other gases at 0 °C are below their respective Boyle temperatures and so they
have Z values less than unity in the low pressure range.

Example 1.11.1 Given that Z = 1.000 54 at 273.15 K and 101.325 kPa pressure and the Boyle temperature
of the gas is 107 K, estimate the values of a and b.
Solution We are given that
Z = 1.000 54, T = 273.15 K, p = 101.325 kPa, and TB = 107 K
From the expression
p Ê a ˆ
Z =1+ b-
RTZ ÁË RT ˜¯
RTZ a
we have b = ( Z - 1) +
p RT
At Boyle temperature, TB = a/Rb so that a = RbTB. Therefore,
RTZ RbTB
b = ( Z - 1) +
p RT
On rearranging, we get

Ê T ˆ Ê Z - 1ˆ
b=Á ˜Á ˜ RTZ
Ë T - TB ¯ Ë p ¯
Substituting the values, we have
Ê 273.15 K ˆ Ê 1.000 54 – 1 ˆ
b=Á (8.314 kPa dm 3 K –1 mol –1 )
Ë 273.15 K – 107 K ˜¯ ÁË 101.325 kPa ˜¯
× (273.15 K) (1.000 54)
= 0.019 9 dm mol –1
3

Also a = RbTB = (8.314 kPa dm 3 K -1 mol -1 ) (0.019 9 dm 3 mol -1 ) (107 K)

= 17.703 kPa dm 6 mol -2

Problem 1.11.1 Express Berthelot and Dieterici equations in the form of virial equation of state and
derive the expressions for the second virial coefficient of these equations. Also derive
the expressions for Boyle temperature.
 Gaseous State 35

Solution Berthelot’s equation

RT a
p= -
Vm - b TVm2
Multiplying by Vm/RT, we get
-1
pVm Vm a Ê bˆ a
Z= = - = Á1 - ˜ -
RT Vm - b Vm RT 2
Ë Vm¯ Vm RT 2
2
b Ê bˆ a
=1+ + Á ˜ + ◊◊◊ -
Vm Ë Vm ¯ Vm RT 2
2
1 Ê a ˆ Ê bˆ
=1+ b- ˜ + Á ˜ + ◊◊◊
Vm ÁË RT 2 ¯ Ë Vm ¯
The second virial coefficient and Boyle temperature are
1/2
Ê a ˆ Ê a ˆ
B = Áb - ˜; TB = Á ˜
Ë RT 2 ¯ Ë Rb ¯
Dieterici’s equation
RT
p= exp(- a/Vm RT )
(Vm - b)
Therefore,
-1
pVm Vm Ê bˆ
Z= = exp(- a/Vm RT ) = Á1 - V ˜ exp(-a/Vm RT )
RT Vm - b Ë m¯

È Ê bˆ
2 ˘È ˘
Í b a 1 Ê a ˆ
= 1+ + Á ˜ + ◊ ◊ ◊˙ Í1 - + ◊ ◊ ◊˙ = 1 + ÁË b - RT ˜¯ + ◊ ◊ ◊
Í Vm Ë m¯
V ˙ Í V RT ˚˙ V
Î ˚Î m m

Thus, the second virial coefficient is (b – a/RT) and Boyle temperature TB is a/Rb.

1.12 CRITICAL CONSTANTS

Andrews Isotherms In 1869, Thomas Andrews carried out an experiment in which p–V relations
of carbon dioxide gas were measured at various temperatures. The types of
isotherms obtained are shown in Fig. 1.12.1. Other real gases also show the
same types of isotherms.
We observe from Fig. 1.12.1 the following:
(1) At high temperatures, such as T4, the isotherms look like those of an
ideal gas.
(2) At low temperatures, the curves have altogether different appearances.
Consider, for example, a typical curve abcd. As the pressure increases, the
volume of the gas decreases (curve a to b). At point b liquefaction commences
and the volume decreases rapidly as the gas is converted to a liquid with a much
higher density. This conversion takes place at constant pressure p. At the point
c, liquefaction is complete and thus the line cd represents the variation of V with
p of the liquid state. The steepness of the line cd is evidence of the fact that the
liquid cannot be easily compressed. Thus, we note that ab represents the gaseous
state, bc, liquid and vapour in equilibrium, and cd shows the liquid state only.
36 A Textbook of Physical Chemistry

Fig. 1.12.1 Andrew’s

graphs of p versus V

Liquefaction commences at b and is complete at c. At a point between b and c,

say X, the ratio of liquid to gas is equal to bX/cX. The pressure corresponding
to the line bc is known as vapour pressure of the liquid.
(3) At still higher temperatures we get a similar type of curve as discussed
in (2) above, except that the width of the horizontal portion is reduced; the
pressure corresponding to this portion being higher than at lower temperatures.
(4) At temperature Tc the horizontal portion is reduced to a mere point.
At temperatures higher than Tc there is no indication of liquefaction at all.
Thus for every gas, there is a limit of temperature above which it cannot
be liquefied, no matter what the pressure is.
Critical temperature Tc is the maximum temperature at which a gas can be
of Critical liquefied, i.e. the temperature above which a liquid cannot exist.
Constants
Critical pressure pc is the minimum pressure required to cause liquefaction at
the temperature Tc.

Critical volume Vc is the volume occupied by one mole of a gas at critical

temperature Tc and critical pressure pc.
Characteristics of The point Y in Fig. 1.12.1 represents the gas in its critical state. At this point
Critical Isotherm the temperature, pressure and volume have critical values. These three are known
as critical constants. The isotherm corresponding to the temperature Tc is known
as critical isotherm. To the left of the point Y on this isotherm, we have the
liquid state whereas to the right, we have the gaseous state. Thus, at point Y
transition from liquid to gaseous state (or vice versa) takes place and thus it
is not possible to state whether the substance is in the gaseous form or in the
liquid form. In fact, both the states become indistinguishable at the critical point.
The surface of separation between liquid and gas disappears. At this point the
various physical properties such as density, refractive index, etc., have identical
values for both the states.
 Gaseous State 37

Experimental Determination of Critical Constants

One of the methods to determine the critical constants Tc, pc and Vc of a gas is
to use the procedure of Andrews, i.e. to plot p–V isotherms for a number of
temperatures. Other methods, which are much simpler are also available.
Determination of Tc The two variables Tc and pc can be determined based on the principle that at
and pc Tc and pc, the densities of liquid and vapour become identical and the surface
of separation—the meniscus between them—disappears.
Bulb A in Fig. 1.12.2, where the substance is placed, is attached to a
mercury manometer B.

Fig. 1.12.2 Apparatus

used for the
determination of critical
temperature and pressure
We adopt the following procedure for obtaining critical values of temperature
and pressure of the gas under examination.
(i) The bulb is cooled so that the surface of separation between the liquid
and vapour is clearly visible.
(ii) Temperature of the thermostat is gradually increased until the meniscus
just disappears. The temperature and the corresponding pressure are noted down.
(iii) The bulb is cooled slowly and again the temperature and pressure at
which the surface of separation just reappears are noted down.
The mean values of the above two temperatures and pressures give the
critical temperature and pressure, respectively.
Determination of Vc The determination of Vc may be carried out by using the law of rectilinear diameter
(given by L. Cailletal and E. Mathias). According to this law, the mean value
of the densities of any substance in the states of liquid and of saturated vapour
at the same temperature is a linear function of the temperature. These densities
where liquid and vapour are in equilibrium are known as orthobaric densities.
Mathematically, we can write
1
(r + rv ) = a + bt
2 1
where a and b are constants. If a graph is drawn between density and temperature;
one obtains a graph of the type shown in Fig. 1.12.3.
Exploring the Variety of Random
Documents with Different Content
9. T* Ἵερεμι. Al.: = Zagagíov. 14. NBCLT*: ἐστάϑη. Et tu cum Jesu
Galikéo eras. ?? At ille negávit coram ómnibus, dicens : Néscio quid
dicis. 7! Exeiünte autem illo jánuam, vidit eum ália ancílla, et ait his
qui erant ibi : Et hic erat cum Jesu Nazaréno, ** Et iterum negávit
cum juraménto : Quia non novi hóminem. *? Et post pusillum
accessérunt qui stabant, et dixérunt Petro : Vere et tu ex illis es :
nam et loquéla tua maniféstum te facit. ** Tune coepit detestári et
juráre, quia non novísset hóminem. Et contínuo gallus cantávit. 75 Et
recordátus est Petrus verbi Jesu, quod díxerat : Prius quam us
cantet, ter me negábis. Et egréssus foras, flevit amáre. XX WVII.'
Maneautem facto, consilium iniérunt omnes príncipes sacerdótum et
senióres pópuli advérsus Jesum, ut eum morti tráderent. ?Et vinctum
adduxérunt eum, et tradidérunt Póntio Piláto præsidi. je ? Tunc
videns Judas, qui eum trádidit, quod damnátus esset, peeniténtia
ductus, rétulit trigínta argénteos principibus sacerdótum et
senióribus, * dicens : Peccávi, tradens sánguinem justum. At illi
dixérunt : Quid ad nos? tu vidéris. * Et projéctis argénteis in templo,
recéssit : et ábiens láqueo se suspéndit, . * Principes autem
sacerdótum, accéptis argénteis, dixérunt : Non licet eos míttere in
corbónam : quia prétium sánguinis est. 7 Consílio autem iníto,
emérunt ex illis agrum figuli, in sepultüram peregrinórum. * Propter
hoc vocátus est ager ille, Hacéldama, hoc est, ager sáninis, usque in
hodiérnum diem. * Tunc implétum est quod dictum est per Jeremíam
prophétam, dicéntem : Et accepérunt triginta argénteos prétium
appretiáti, quem appretiavérunt a filiis Israel : '? et dedérunt eos in
agrum figuli, sicut constítuit mihi Dóminus. T 11 Jesus autem stetit
ante présidem, et interrogávit eum praeses, is : Tu "4. Servante n'est
pas dans le grec. XXVII. 8. Grec : « c'est pourquoi ce champ fut
appelé le champ du sang jusqu'aujourd'hui ». | 9-40, Ces versets
figurent entre parentheses dans le grec. εἰ
 Matthieu, XXVI, 70 — XXVII, 11. 133 léen? » 7% Mais il nia
devant tous, 735 95; disant : > Je ne sais ce que tu veux Le 5 5.
dire .‫ג‬‎7! Et comme il sortait hors at. 31, 11. , Joa. 15, 5. de la
porte, une autre servante l'a- mur 14, 69, percut et dit à ceux quise
trouvaient là : « Celui-ci était aussi avec Jésus de Nazareth ». 75 Et
il le nia jit 15:5. de nouveau avec serment, disant : : > Je ne connais
point cet homme ». 73 Peu après, ceux qui se trouvaient 29.25 s».
là s’approchèrent et dirent à Pierre : « Certainement, toi aussi tu es
de ces gens-là: ton langage te décèle ». 74 Alors il se mit à faire des
im- 4. 33,3. précations et à jurer qu'il ne con- ^^ ^* naissait point
cet homme. Et aussitôt un coq chanta. 7* Et Pierre se 1 cor. 155.
souvint de cette parole que Jésus lui ἘΣ οἱ, s: avait dite: > Avant
qu'un coq chante, πῶς 5 tu me renieras trois fois ». Et étant ἴα, 3,
31. sorti, il pleura amérement. , X€XWIE ' Or le matin étant ‫ל‬‎venu,
tous les princes des prétres ‫ו‬‎,. , et les anciens du peuple tinrent 1:5;
conseil contre Jésus, pour 16 livrer à 302.15, 38. la mort. ? Et l'ayant
lié, ils l'emme- 7221 nerent et le livrérent à Ponce Pilate, sr. 3, 30.
erneur. mnm 3 Alors Judas, qui l'avait = Judas ee ut^?" voyant qu'il
était condamné, touché de repentir et reporta les Me trente pièces
d'argent aux princes ; 15. des prêtres et aux anciens, * « pr
nousimporte? Vois toi-même». 41.1. 5 Alors ayant jeté l'argent dans
le 6 Co, 3, 7. ils en achetèrent le champ du potier, pour la sépulture
des étrangers. * C'est pourquoi ce champ est encore aujourd'hui
appelé Haceldama, c'est-à-dire le champ du sang.*Alors fut
accomplie la parole du prophète Jérémie, disant: « Ils ont recu les
trente pièces d'argent, prix de celui - quiaété apprécié suivant
l'apprécia— ton des enfants d'Israél;'? et ils les ont données pour le
champ du potier, ainsi que me l'a prescrit le Seigneur ». cd . '' Or
Jésus comparut devant le tac. - gouverneur, qui linterrogea, di- τως.
35,2 - sant: > Es-tu le roi des Juifs ? » Jé- 35217 Act. 1, 19. Zach.
11, 12. Jer. 32, 6; 19, 2. Joa. 36, 17. 73. Ton langage te décèle. Les
Galiléens n'avaient pas le méme accent que les habitants de
Jérusalem et de la Judée. Le Talmud dit que leur langage était
corrompu et qu'ils brouillaient μὰ ii aen les unes avecles autres : le 5
avec le , 6 Cc. t de saint Pierre πὸ. Et étant sorti, il pleura
amérement. Selon la tradition, saint Pierre alla pleurer son péché
dans une grotte, transformée en tombeau et située sur le versant de
la partie du mont Sion qui regarde la vallée du Cédron. On éleva
dans la suite, au-dessus de cette grotte, une église que les anciens
pélerins nomment Gallicante ou le Chant du coq. XXVII. 1. Les
princes des prêtres et les anciens du ety oes Voir plus haut la note
sur xxv1,3. 2. « Ponce-Pilate fut le cinquieme procurateur envoyé de
Rome en Judée. Il gouverna cette province de l'an 26 à l'an 36 de
l'ére chrétienne, sous les ordres du légat de Syrie. C'était une
créature de Séjan, favori de 110676. Par ménagement pour la
susceptibilité des Juifs, il résidait à Césarée de Palestine, place forte
sur la côte de la mer; mais, comme Antipas, il venait à Jérusalem au
temps des grandes fétes, et alors il habitait le prétoire, demeure
contigué au palais d'Hérode et à la tour Antonia ». (L. Bacuez). 3-10.
Mort de Judas. Trait propre à saint Matthieu. 6. Le trésor était
l'endroit du temple oü le peuple mettait ses présents et ses
offrandes. 1. Du potier ; c'est-à-dire du potier de ce lieu. 8.
Haceldama, cest-à-dire le champ du sang. L'emplacement
traditionnel de ce champ, qui porte toujours le méme nom, est au
sud de Jérusalem, sur le versant méridional de la vallée de Ben-
Hinnom. 9. Le texte qui est rapporté ici ne se lit pas dans Jérémie;
mais on en trouve la substance dans Zacharie. Saint Matthieu a pu
se borner à dire du prophète, sans ajouter aucun nom. Il est certain
que la version syriaque et plusieurs anciens manuscrits latins ne
nomment pas le prophète. Cependant les interprètes ne conviennent
pas tous que saint Matthieu ait fait cette omission, et ils cherchent à
maintenir, les uns le nom de Jérémie, les autres celui de Zacharie
(Glaire). 11-14. Jésus devant Pilate. Comparer avec Marc, xv, 2-5;
Luc, xxui, 2-5; Jean, xvii, 29-38.
 134 Matthæus, XXVII, 12-29. Ultima Jesu (XXI-XXVIII). —
4^ Passio Christi ( XXVI, 36-XXVII).‫צוו‬. ‫‏‬δαίων; 'O di "100006 ἔφη
αὐτῷ" Σὺ λέγεις. 13 Καὶ ἐν τῷ κατηγορεῖσϑαι αὐτὸν ὑπὸ τῶν
ἀρχιερέων καὶ τῶν πρεσβυτέρων, οὐδὲν ἐπεκρίνατο. 1015 λέγει
αὐτῷ 6 Πιλᾶτος" Οὐχ ἀκούεις, πόσα σου χαταμαρτυροῦσι; '5 Καὶ ovx
ὠπεχρίϑη αὐτῷ πρὸς οὐδὲ ἕν ῥῆμα, ὥςτε θαυμάζειν τὸν ἡγεμόνα
λίαν. ! Kara δὲ ἑορτὴν εἰώϑει ὃ ἡγεμωὼν ἀπολύειν ἕνα τῷ ὄχλῳ
δέσμιον, ὃν ἤϑελον. ἐδ Εἶχον δὲ τότε δέσμιον ἐπίσημον, λεγόμένον
Βαραββᾶν. 17 Συνηγμένων οὖν αὐτῶν, εἶπεν αὐτοῖς ὃ Πιλᾶτος: Τίνα
ϑέλετε ἀπολύσω ὑμῖν, Βαραββᾶν ἢ Ἰησοῦν τὸν λεγόμενον Χριστόν; δ
ἤδει γώρ, ὅτι διὰ φϑόνον παρέδωχαν αὐτόν. 1 Καϑημένου δὲ αὐτοῦ
ἐπὶ τοῦ βήματος, ἀπέστειλε πρὸς αὐτὸν ἡ γυνὴ αὐτοῦ, λέγουσα.
Mndér σοι xoi τῷ δικαίῳ ἐκείνῳ" πολλὰ γὰρ ἔπαϑον σήμερον xar'
ὄναρ δι᾽ αὐτόν. δ δὲ ἀρχιερεῖς καὶ οἱ πρεσβύτεροι ἐπεισὰν τοὺς
ὕχλους, ἵνα αἰτήσωνται τὸν Βαραββᾶν, τὸν δὲ ᾿Ιησοῦν ἀπολέσωσιν.
21 ᾿Αποχριϑεὶς δὲ 6 ἡγεμὼν εἶπεν αὐτοῖς" Τίνα ϑέλετε ἀπὸ τῶν δύο
ἀπολύσω ὑμῖν; Οἱ δὲ εἶπον" Βαραββᾶν. 33 «“Ἵέγει αὐτοῖς ὃ Πιλᾶτος"
Ti οὖν ποιήσω "Inoobv τὸν λεγόμενον “Χριστόν; Aéyovouw αὐτῷ
πάντες" Σταυρωϑήτω. “5 Ὁ δὲ ἡγεμων ἔφη" Τί γὰρ κακὸν ἐποίησεν;
Où δὲ περισσῶς ἔχραζον, λέγοντες" Σταυρωϑήτω. 21 dur δὲ 6
Πιλᾶτος, ὅτι οὐδὲν ὠφελεῖ, ἄλλα μᾶλλον ϑόρυβος γίνεται, λαβὼν
ὕδωρ ἀπενίψατο τὰς χεῖρας ἀπέναντι τοῦ ὄχλου, λέγων" ᾿ϑῶδς εἶμι
ὠπὸ τοῦ αἵματος τοῦ δικαίου τούτου" ὑμεῖς ὄψεσϑε. 3" Καὶ ἀποκριϑ
εὶς πᾶς ó λαὺς ene Τὸ αἷμα αὐτοῦ ἐφ᾽ ἡμᾶς καὶ ἐπὶ τὰ τέχνα ἡμῶν.
35 Τότε ἀπέλυσεν αὐτοῖς τὸν Βαραββᾶν, τὸν δὲ Ἰησοῦν
φραγελλώσας παρέδωχεν, ἵνα σταυρωϑῆ. 9' Τότε οἱ στρατιῶται τοῖ
ἡγεμόνος, παραλαβόντες τὸν ᾿Ιησοῦν εἰς τὸ πραιτώριον, συνήγαγον
ἐπ᾿ αὐτὸν ὅλην τὴν σπεῖραν. 35 Καὶ ἐχδύσαντες αὐτόν περιέϑηχαν
αὐτῷ a , b 0 χλαμύδα κοχχίνην, * xal πλέξαντες στέφα12. RBT?*
(sec. )rwr.1 65. ΤΊ : Ἰησοῦν Βαραββᾶν (bis). 20. XT (p. πρεσβ.) τοῦ
λαοῦ. 91. DT: εἷπεν. 22. NABDT* αὐτῷ. 23. NBT* ἡγεμών. 2%
BDLT*: κατέναντι. BDILIT* τοῦ dix. 98. L: ἐγδύσ. s es rex
Judæérum? Dicit illi Jesus : Tu dicis. '* Et cum accusarétur a
princípibus sacerdótum et senióribus, nihil respóndit. '* Tune dicit illi
Pilátus : Non audis quanta advérsum te dicunt testimónia? '* Et non
respóndit ei ad ullum verbum, ita ut mirarétur præses veheménter. '5
Per diem autem solémnem consuéverat præses deme dimíttere
unum vinctum, quem voluíssent : '* habébat autem tunc vinetum
insígnem, qui dicebátur Barábbas. '' Congregátis e illis, dixit Pilátus :
Quem vultis didit. vobis : Barábbam, an Jesum qui dícitur Christus?
'* Sciébat enim per invídiam tradidíssent eum. '? Sedénte autem illo
pro tribunáli, misit ad eum uxor ejus, dicens : Nihil tibi, et justo illi :
multa enim passa sum hódie per visum propter eum. 8 ?? Principes
autem sacerdótum et senióres persuasérunt pópulis ut péterent
Barábbam, Jesum vero pérderent. ?! Respóndens autem præses, ait
illis : quem vultis vobis de duóbus dimítti? At illi dixérunt :
Barábbam. 33 Dicit illis Pilátus : Quid ígitur fáciam de Jesu qui dicitur
Christus ??? Dicunt omnes : Crucifiátur. Ait illis praeses : Quid enim
mali fecit? At illi magis clamábant, dicéntes : Crucifigátur. *: Videns
autem Pilátus quia nihil proficeret, sed magis tumultus fieret,
accepta aqua, lavit manus coram pópulo, dicens : Innocens ego sum
a sánguine justi hujus : vos P essct 38 - respóndens univérsus
ópulus, dixit : Sanguis ejus super nos. et 5 er 8 situe Tune dimísit
illis Barábbam : Jesum autem flagellátum trádidit eis ut
crucifigerétur. — 27 Tunc milites præsidis suscipiéntes Jesum in
prætérium, congregavérunt ad eum univérsam cohórtem : ?* et
exuéntes eum, chlámydem coccíneam circumdedérunt ei, ?* et
plecténtes corónam de spi15. A un des jours de la féte solennelle.
Grec : « durant la fête = 16. Il avait. Grec : « ils avaient ». 41. Pilate
dit. Grec : « Pilate leur dit ». 23, Le commencement du verset est
rattaché dans le grec au verset 23. RS - 23 311 1 "i ch, U^ URT UV.
|:=
 = Matthieu, XXVII, 12-29. 135 Derniers jours (X XI-X
XVIII). — 3* La Passion CXXVI, 36- XXVII).‫וון‬. ‫‏‬sus lui répondit : >
Tu le dis ». "57 17.27. 12 Et comme les princes des prêtres 3er τὸ, 3.
et les anciens l'accusaient, il ne ré- 3o 18, 35; pondit rien. !? Alors
Pilate lui dit : 163,1 Pas, 2. « N'entends-tu point combien de té- xcu.
ss, 6. moignages ils rendent contre toi? » 1% Mais il ne répondit à
aucune de r. 31,4. ses paroles, de sorte que le gouverneur en était
extrémement étonné. 15 À un des jours de la fête so- marapbas
lennelle, le gouverneur avait cou- opponitur. tume de délivrer au
peuple un prison- Wo wo nier, celui qu'ils voulaient. 1% Or il 795.
15, 39. avait alors un prisonnier insigne "^*^ '* nommé Barabbas.
‘7 Le peuple étant donc assemblé, Pilate dit : « Lequel voulez-vous
Ly je vous délivre, Barabbas ou Jésus, qui est appelé : Christ? » 48
Car il savait que c'é- ὅρα issu tait par envie qu'ils l'avaient livré. 19
Or, pendant qu'il siégeait sur , Uxer son tribunal, sa femme lui
envoya "n. 5, # dire: > Qu'il n'y ait rien entre toi et 75» ss i ce juste;
car j'ai beaucoup souffert ?* 5?" aujourd'hui dans un songe à cause
de lui ». 2 Mais les princes des prétres parabbas. et les anciens
persuadèrent au peuple ‫זג‬‎15, τι. de demander Barabbas, et de faire
‫ל‬‎is 40. périr Jésus. ? Le gouverneur donc i427 jenen la parole, leur
dit : > Lequel 577 157 es deux voulez-vous que je vous τος 23, 15.
délivre? » Ils répondirent : > Barab- 545: bas ». ?* Pilate leur
demanda : «Que 75 9. 5, 15. ferai-je donc deJésusappelé Christ?» —
: ^ ?3 [ls s'écrièrent ious : > Qu'il soit ss 3, 90. crucifié! » Le
gouverneur leur re- Mer 16, 1« partit: > Quel mal a-t-il fait? » Mais
os. 15, 46. ils criaient encore plus, disant : « Qu'il soit crucifié! » **
Pilate voyant qu'il ne gagnait Crucifisenrien, mais que le tumulte
augmen- traditur 1 1 esu tait, prit de l’eau et se lava 1068 35. δ.
Deut. 31, 6. mains devant le peuple, disant : « Je suis innocent du
sang de 06 31. juste : voyez vous-mémes ». 25 Et Mar. ss ss. _ tout
le peuple répondant, dit : > Son xx %, sx sang sur nous et sur nos
enfants | » 7*5 56 Alors il leur délivra Barabbas; y. 15 15. mais
Jésus, aprés l'avoir fait flagel- Le 25 2i. En il le leur livra pour être
cruci- 2 37, 18. é. 1 Aussitôt les soldats du gou- coronatur verneur
menant Jésus dans le pré- iu«ditar. toire, rassemblérent autour de lui
15, 16. toute la cohorte; ?* et, l'ayant dé- ἀεὶ. 385,36. pouillé, ils
l'enveloppérent d'un man- »-: teau d'écarlate; ?? puis tressant
25:92. une couronne d'épines: ils la mirent + ris à. 15-26. Barabbas
préféré à Jésus. Comparer avec Marc, xv, 645; Luc, xx, 13-25; Jean,
xvin, 39-40. 45. A un des jours de la fête. solennelle; c'est-àdire
pendant la fête de Pâque (Cf. Jean, xvii, 39). Comme c'était la plus
grande de leurs solennités, les Juifs la désignaient assez
ordinairement sous le nom de ἴα fête. 16. Barabbas, d'apres les
détails fournis par les divers évangélistes, avait trempé dans une
sédition, et il était voleur et assassin. 19. Sa femme, Claudia Procula
ou Procla, d'apres la tradition. 24. Les paiens aussi se lavaient les
mains, soit dans les alliances, soit dans les sacrifices qu'ils offraient
aux dieux supérieurs, soit enfin pour expier un meurtre ou se purifier
du sang répandu méme à la guerre; mais on pense généralement
que Pilate a voulu dans cette circonstance se conformer à l'usage
des Juifs pour leur étre agréable (Glaire). 96-31. Flagellation et
couronnement d'épines. Comparer avec Marc, xv, 16-20; Jean, xix,
1-3. 96. Le supplice de la croix était la peine des esclaves, des
voleurs, mais surtout des séditieux, suivant les lois romaines. Les
Hébreux, selon Maimonide, ne crucifiaient réguliéerement pas les
hommes en vie, mais aprés leur mort; ils les attachaient au poteau
et les en détachaient avant le coucher du soleil. Cf. Deutéronome,
XXI, ME: A .‫דפ‬‎Menant Jésus dans le prétoire. Le prétoire qui
désigna d'abord la tente du général en chef ans le camp, fut aussi
plus tard le nom donné à la résidence d'un gouverneur de province,
comme était Pilate. C'est là qu'il habitait et qu'il rendait la justice.
Les évangélistes ont conservé le nom latin grécisé que les Latins
avaient donné au palais du procurateur dans la capitale de la Judée.
A la place oü s'élevaitautrefois le Prétoire est aujourd'hui en grande
partie, à ce qu'on croit, la cour actuelle de la caserne turque, au
nordouest du Temple. On y voit encore de grosses pierres qu'on dit
avoir appartenu au prétoire. > L’escalier, qui, de la cour supérieure
ou était le prétoire, conduisait dans la cour inférieure occupée
aujourd'hui pàr une rue, a été transporté à Rome, où il est vénéré
près de Saint-Jean de Latran ». (J. H. Michon). — La cohorte
romaine se composait de six cent vingt-éinq hommes. 28. Ils
l'enveloppérent d'un manteau d'écarlate. En grec et en latin: d'une
chlamyde. C'était une espece de manteau de laine, ouvert et
retroussé sur l'épaule gauche, où il s'attachait avec une agrafe, afin
de laisser le bras droit libre. Ce nom, d'origine grecque, il désigne ici
le paludamentum, vêtement militaire des soldats romains. I! était de
forme ovale, se portait pardessus la cuirasse et retombait en arriére,
à peu près jusqu'à mi-jambe. Les tribuns le portaient de couleur
blanche; les généraux et les empereurs de couleur pourpre. 29. Une
couronne d'épines. La couronne qu'on mit sur la tête de Notre-
Seigneur était de jones, entrelacés d'épines de zizyphus. La
couronne proprement dite est conservée à Notre-Dame de Paris;
Pise possede dans sa jolie église de la Spina une branche de
zizyphus. La couronne de jones de Paris, > cette relique insigne,
peutétre la plus remarquable de celles que possédent les chrétiens,
à cause de son intégrité relative, vient sans conteste de saiat Louis.
Elle se compose d'un anneau de petits jones réunis en faisceaux. Le
diamètre intérieur de l'anneau est de 910 millimètres, la section a 15
millimètres de diamètre. Les jones sont reliés par quinze ou seize
attaches de joncs semblables. Quelques jones sont pliés et font voir
que la plante est creuse ; leur surface, examinée à la loupe, est
Sillonnée de petites côtes. Le jardin des Plantes de Paris cultive un
jonc appelé juncus balticus, originaire des pays chauds et qui paraît
exactement semblable à la relique de Notre-Dame. ‘Quant aux
épines, nul doute que ce ne soit du rhamnus, nom générique de
trois plantes qui se rapprochent tout à fait de l'épine de Pise. Ce
rhamnus était le zizyphus spina Christi ou ju 
 136 Matthæus, XXVII, 30-37. ἘΠΕ. Ultima Jesu (XXI-
XXWIIN). — 3 Passio Christé (XXVI, 36-XXVID. voy ἔξ ὠχανϑῶν
ἐπέϑηκαν ἐπὶ τὴν κεφαAny αὐτοῦ, καὶ κάλαμον ἐπὶ τὴν δεξιὼν
αὐὖτοῦ, καὶ γονυπετήσαντες ἔμπροσϑεν αὐτοῖ ἐνέπαιζον αὐτῷ
λέγοντες" Χαῖρε, ὅ βασιλεὺς τῶν Ἰουδαίων, 35 καὶ ἐμπτύσαντες εἰς
αὐτὸν ἔλαβον τὸν κάλαμον καὶ ἔτυπτον εἰς τὴν κεφαλὴν αὐτοῦ. 31
Καὶ ὅτε ἐνέπαιξαν αὐτῷ, ἐξέδυσαν αὐτὸν τὴν χλαμύδα, καὶ ἐνέδυσαν
αὐτὸν τὰ ἱμάτια αὐτοῖ, καὶ ἀπήγαγον αὐτὸν εἰς τὸ σταυρῶσαι. 33
Ἐξερχύμενοι δὲ εὗρον ἄνθρωπον Κυρηναῖον, ὀνόματι Σίμωνα"
τοῦτον ἠγγάρευσαν, ἵνα ἄρῃ τὸν σταυρὸν αὐτοῖ. 38. Kai ἐλθϑύντες
εἰς τόπον λεγόμενον Γολγοθᾶ, ὅς ἐστι λεγόμενον κρανίου τόπος, 31.
ἔδωχαν αὐτῷ πιεῖν ὄξος μετὰ χολῆς μεμιγμένον" καὶ γευσάμενος οὐχ
ἤϑελε πιεῖν. 95 Σταυρώσαντες δὲ αὐτόν, διεμερίσαντο τὰ ἱμύτια
αὐτοῦ, βάλλοντες κλῆρον ἵνα πληρωϑῇ τὸ δηϑὲν ὑπὸ τοῦ προφήτου"
Zhsμερίσαντο vC ἱμάτιά μου ξαυτοῖς, καὶ ἐπὶ τὸν ἱματισμόν μου
ἔβαλον κλῆρον. 35 Kai χαϑήμενοι ἐτήρουν αὐτὸν ἐχεῖ. ‫זל‬‎Kai > , ‫כ‬‎,
- - )[ - MJ ἐπέϑηχαν ἐπάνω τῆς κεφαλῆς αὐτοῦ τὴν Entrée de Notre-
Soigneur à Jérusalem 10 di nis, posuérunt super caput ejus, et
aründinem in déxtera ejus. Et genu flexo ante eum, illudébant ei,
dicéntes : Ave rex Judæérum. * Et expuéntes in eum, accepérunt
aründinem, et percutiébant caput ejus. ?! Et postquam illusérunt ei,
exuérunt eum chlámyde, et induérunt eum vestiméntis ejus, et
duxérunt eum ut crucifigerent. 33 Exeüntes autem invenérunt
hóminem Cyren&um, nómine Simónem : hune angariavérunt ut
tólleret crucem ejus. 33 Et venérunt in locum qui dicitur Gólgotha,
quod est Calväriæ locus. *! Et dedérunt ei vinum bíbere cum felle
mistum. Et cum gustásset, nóluit bíbere. ?5 Postquam autem
crucifixérunt eum, divisérunt vestiménta ejus, sortem mitténtes : ut
implerétur quod dictum est per prophétam dicéntem : Divisérunt sibi
vestiménta mea, et super vestem meam misérunt sortem. ?* Et
sedéntes servábant eum. ?? Et imposuérunt super caput ejus (XXI,
5, p. 97), (D'après des R une miniature du manuscrit des y een de
Rosmno), 2 mt ἢ δὴ D LEM. elm € 7 xe. τόπ. » NBDL DEAN de prt T
35. NADLT : βαλόντες. G(K)SLT[HG* ἵνα-κλῆρ.
 Matthieu, XXVII, 30-37. 137 ἘΠῚ. Derniers jours (XXI-
XXVIIE). — 3» La Passion C XXVI, 36- XXVII). sur sa téte, et un
roseau dans sa main droite ; et fléchissant le genou devant lui, ils le
raillaient, disant : > Salut, roi des Juifs ». 9% Et, crachant sur lui, ils
prenaient le roseau, et en frappaient sa téte. 91 Aprés qu'ils se
furent ainsi Pueitur ad joués de lui, ils lui otérent le man- ,,, ,; 67.
teau, 16 couvrirent de ses vêtements, Philip 3, 5. et l'emmenérent
pour le crucifier. y. 13, 12. 33 Or, comme ils sortaient, ils ren- Mare.
15, 21. contrèrent un homme de Cyrene, ;, 19, 17. nommé Simon;
ils le contraignirent P7 5 de porter sa croix. 3% Et ils vinrent au lieu
appelé Golgotha, qui estle lieu du Calvaire. 35 Là, ils lui donnèrent à
boire du vin mélé avec du fiel; mais lorsqu'il eut goüté, il ne voulut
pas boire. 55 Après qu'ils l'eurent crucifié, pivisæ ils partagèrent ses
vêtements, je- me 13, 2. tant le sort, afin que fût accomplie 575 is s
la parole du prophète, disant : «Ils 27557 se sont partagé mes
vêtements, et 3212. 38. Crucifigitur. Joa. 19, 29, 30. Lue. 16, 24. Ps.
68, 22; jubier. Dans la couronne de Notre-Seigneur, ses] branches
brisées ou courbées vers le milieu pour prendre la forme d'un
bonnet, étaient fixées par chacune de leurs extrémités, soit en
dedans, soit au dehors du cercle de joncs. Il fallait que le cercle füt
plus grand que le tour de la tête, afin de pouvoir l'y faire entrer,
malgré le rétrécissement causé par l'introduction des branches, et
l'on trouve en effet que la couronne de Notre-Dame placée seule sur
la téte tomberait surles épaules.. On n'avait méme pas besoin de
nouveaux liens pour les fixer au cercle de joncs; et les rameaux
passés alternativement dessus et dessous devaient suflire pour les
maintenir. C'est cette opération que les [évangélistes] ont pu appeler
le tressage. Les soldats sans doute, évitèrent de toucher à ces
horribles épines, dont chacune plus tranchante que la griffe du lion
fait jaillir le sang en abondance. |La branche de zizyphus de Pise] a
80 millimètres de hauteur. L'épine principale a plus de 20 millimètres
de longueur ». (Rohault de Fleury). 32-38. Crucifiement. Comparer
avec Mare, xv, 22-98; Luc, xxut, 33; Jean, xix, 11-24. 32. Sa croir.
Les auteurs avaient émis les opinions les plus diverses sur la nature
du bois ou des bois dont était formée la croix. Aprés l'examen
scientifique de diverses reliques, « on peut affirmer que le bois de la
croix provenait d'un conifère, et on ne peut douter que ce conifère
ne soit du pin. [D'apres l'opinion commune, l'instrument du supplice
de Notre-Seigneur se composait d'un montant] avec une traverse
laissant passer la téte de la tige, comme l'usage dela représenter
s'en est le plus généralement répandu. ες gh 21,19. | [D’après] une
ancienne tradition, la hauteur du sur ma robe, ils ont jeté le sort ».
MOINE etit de à métres 80, et celle de la 36 Dao eZ git - raverse de
2 mètres 30 à 2 mètres 60 ». Le supPuis s'étant assis, ils le
gardaient. Para plice de la croix, très fréquent chez les Romains,
était spécial pour les esclaves. On l'appliquait quelquefois aux
hommes libres, mais alors aux plus vils ou aux plus coupables,
comme les voleurs, les assassins, les faussaires. Chez les Romains,
les condamnés portaient leur croix. Plaute a dit : qu'il porte la
potence à travers la ville et qu'il soit ensuite attaché à la croix. «
L'intervention de Simon le Cyrénéen peut s'entendre de deux
manieres. Le texte sacré ne dit pas formellement si Notre-Seigneur
fut totalement déchargé de sa croix, ou s'il continua à la porter avec
une aide étrangère. Dans la première hypothèse, le Christ aurait
marché en avant, Simon portant seul la croix en arrière. Dans la
seconde, il aurait porté la partie antérieure et Simon la "n"
postérieure, le bout trainant à terre. Saint Augustin, saint Athanase,
saint Jéróme, saint Léon, gene et plusieurs modernes supposent que
Notre-Seigneur fut entierement déchargé. [On peut donner] à la
croix un [poids total] d'environ cent kilogrammes. La croix devait
trainer à terre, [parce que] ce long bois n'aurait pu rester en
équilibre sur l'épaule;la diminution de poids qui en résultait peut étre
évalué à 250u 30 kilogrammes. [Le Sauveur avait donc encore à
porter] environ 75 kilogrammes. [Ce fardeau dépassait ses forces,
parce qu'il était] épuisé par les supplices qu'il avait endurés, par la
longueur de la voie douloureuse dont on connaît au moins les deux
extrémités el qui devait être de 5 à 600 mètres, et par la difficulté
des chemins dans un sol montueux ». (Rohault de Fleury). 33.
Golgotha. Le Golgotha est actuellement enclavé dans l’église du
Saint-Sépulcre, dans la partie sudest de la Basilique. II s'élève à la
hauteur de 4 metres 70 centimètres au-dessus du sol. Du temps de
Notre-Seigneur, le Calvaire était en dehors de Jérusalem, à l'ouest ;
aujourd'hui il est dans l'enceinte même de la ville. 34. Du vin mélé
avec du fiel. Voir la note sur Jean, χιχ, 29-30. 35. A qu'ils l'eurent
crucifié. « Tantót la victime était attachée par terre à la croix, qui
était ensuite élevée avec son fardeau; tantôt la croix était d'abord
dressée, et le condamné attaché avec des cordes, puis cloué. Le
premier mode parait avoir été plus probablement employé sur le
Calvaire. Les €rucifiés étaient souvent fixés avec des clous [placés au
milieu des mains et aux — Avant de clouer les pieds, on préparait le
trou avec une broche. Ce que dit le Sauveur à saint Thomas Jean,
xx, 21) prouve qu'il avait eu les mains percées de clous. Les auteurs
profanes qui se sont occupés du crucifiement parlent toujours de
quatre clous. Toutes les peintures grecques representent Notre-
Seigneur fixé sur la croix avec quatre clous. Le clou [de la passion
conservé Al Notre Déni [de Paris, de 90 millimètres de longueur, n'a
pas de tête; sa pointe méplate est intacte. La forge en est grossière.
Le clou que l'on voit dans la basilique de Sainte-Croix de Jérusalem à
Rome a 120 millimètres de long, 8 millimètres 1/2 de grosseur à sa
plus grande dimension, et sa tête est couverte d'une espèce de
chapeau creux au fond duquel il est rivé, comme on le voit à
quelques clous antiques, à ceux par exemple de la Bibliothéque du
Vatican ». (Rohault de Fleury). . 91. Celui-ci est Jésus, le roi des
Juifs. > Un écriteau destiné à faire connaitre les motifs de la
condamnation [était] porté en avant du condamné, ou attaché à son
cou; il était parfois remplacé par une proclamation du crieur public,
annonçant le nom du criminel et l'arrét de la justice. Il était préparé
quand NotreSeigneur sortit du prétoire, afin de le précéder dans le
long parcours de la voie douloureuse. Le titre ne tenait pas encore à
la croix, à laquelle il ne fut attaché avec des clous que sur le Calvaire
». Les trois premiers évangélistes n'ont pas rapporté mot à mot
l'inscription; ils n'en ont donné que le sens. Saint Jean est le seul qui
l'ait littéralement reproduite, en nous apprenant qu'elle portait ces
mots: Jésus de Nazareth, roi des Juifs, écrits en trois langues, en
hébreu ou araméen, en grec et en latin. L'église de Sainte-Croix de
Jérusalem, à Rome, possède un fragment considérable du titre de la
croix. « C'est une petite planche [de chéne ou bien de sycomore ou
de peuplier] de 935 millimétres de largeur sur 130 millimetres de
hauteur, sillonnée de trous de vers. On y voit trés distinctement deux
restes d'inscription grecque et romaine, et dans le haut, l'extrémité
de quelques lignes courbes qui paraissent étre ceux d'une troisieme
inscription [en lettres hébraiques] La seconde inscription porte :
Nazarenous (en caractères grecs) et la troisième : NazanENus RE.
Les lettres sont légèrement en creux, comme si elles avaient été
tracées avec cet outil particulier dont les charpentiers se servent de
nos jours pour marquer le bois, ou simplement avec une petite
gouge. Elles ont de 98 millimètres à 30 millimétres. Peintes en rouge
sur un fond blanc. 31 Et ils mirent au-dessus de sa tête
 138 Matthæus, XXVII, 38-54. .‫וו‬‎Ultima Jesu (XXE-XXWIII).
— # Passio Christi (XXVI, 36-XX VII): αἰτίαν αὐτοῦ γεγραμμένην"
Οὗτός ἔστιν | causam ipsíus scriptam : Hic ssr Jesus Ἰησοῦς 6
βασιλεὺς τῶν Ιουδαίων. 88. "Tire σταυροῦνται σὺν αὐτῷ 060 λησταί,
εἷς à δεξιῶν καὶ εἷς ἐξ εὐωνύ 2 39 Οἱ δὲ παραπορευόμενοι
ἐβλαςφήμουν αὐτόν, κινοῦντες τὰς χεφαλὰς αὑτῶν "xoi λέγοντες" Ὁ
καταλύων τὸν ναὸν καὶ ἐν τριoir ἡμέραις οἰκοδομῶν, σῶσον
σεαυτόν" ci υἱὸς εἶ τοῦ ϑεοῖ, κατάβηϑι ἀπὸ τοῦ σταυgov. ^ Ὁμοίως
δὲ καὶ où ἀρχιερεῖς ἐμσιαίζοντες μετὰ τῶν γραμματέων xol
πρεσβυτέρων ἔλεγον" “5 Ἄλλους ἔσωσεν, ξαυτὸν où δύναται σῶσαι"
εἰ βασιλεὺς Ἰσραήλ ἐστι, καταβάτω ‫עטע‬‎ἀπὸ τοῦ σταυροῖ, καὶ
πιστεύσομεν αὐτῷ. 13 Πέποιϑεν ἐπὶ τὸν ϑεόν' δυσάσϑω γῦν αὐτόν,
εἰ ϑέλει αὐτόν" eine ydp Ὅτι ϑεοῦ εἰμὶ viog. “Τὸ δ᾽ αὐτὸ χαὶ οἱ λῃσταὶ
οἱ συσταυρωϑέντες αὐτῷ ὠνείδιζον αὐτῶ. 5 dà δὲ ἕκτης ὥρας
σχότος ἐγένετο ἐπὶ πᾶσαν τὴν γῆν ἕως ὥρας ἐννάτης. 46 Περὶ δὲ τὴν
ἐννάτην ὥραν ἀνεβόησεν 0 Ἰησοῦς φωνῇ μεγάλῃ, λέγων" "HA AL
λαμὰ σαβαχϑανί; τουτέστι. Θεέ μου, ϑεέ μου, ἱνατί με ἐγκατέλιπες;
11 Τινὲς δὲ τῶν ἐχεῖ ἑστώτων ἀκούσαντες ἔλεγον" Ὅτι Ἠλίαν φωνεῖ
οὗτος. 55 Καὶ εὐἰϑέως δραμὼν εἷς ἐξ αὐτῶν καὶ λαβὼν σπόγγον,
mous τε 0506 καὶ περιϑεὶς καλάμῳ, ἐπότιζεν αὐτόν. "Oi δὲ λοιποὶ
ἔλεγον" Aes, ἴδωμεν εἰ ἔρχεται Ἡλίας σώσων αὐτόν. 500 δὲ Ἰησοῦς
πάλιν κρώξας φωνῇ μεγάλῃ, ἀφῆκε τὸ πνεῦμα. 51 Καὶ ἰδού, τὸ
καταπέτασμα τοῦ ναοῦ ἐσχίσϑη εἰς δύο dnd ἄνωϑεν ἕως κάτω, καὶ ἡ
γῆ ἐσείσϑη, καὶ αἱ πέτραι ἐσχίσϑησαν, καὶ τὰ μνημεῖα ἀνεύχϑησαν,
καὶ πολλὰ σώματα τῶν κεκοιμημένων ἁγίων ἠγέρϑη, 58 vol
ἐξελϑόντες à ἐχ τῶν uv ἡμείων μετὰ τὴν ἔγερσιν αὐτοῦ εἰςῆλϑον εἰς
τὴν ἁγίαν πόλιν, καὶ ἐνεφανίσϑησαν πολλοῖς. MO δὲ ἑκατόνταρχος
χαὶ οἱ μετ᾽ αὐτοῦ τηροῦντες τὸν "moovv, ἰδόντες τὸν σεισμὸν καὶ τὸ
γενόμενα, ἐφοβήϑησαν σφόδρα, λέ39. E* αὐτόν. 40. L: oeavr.
NADT?: καὶ κατάβ. 2 M. NA[L]T* δὲ xci. 42. NBDT* εἰ. AL: m.
oredouer. EG'KSO: ἐπ᾿ αὐτῷ. NBT: ἐπ’ αὐτόν ὌΠ ras ἐπὶ τῷ 9. NBT?*
(pr.) αὐτὸν. 44. NABD ὟΣ αὐτὸν. 46. LT: "HA A (T*: Ἡλεὶ) λημὰ
οαRex Jupæonum. ?* Tunc crucifíxi sunt cum eo duo latrónes : unus
a dextris, et unus a sinistris. M ?? Prætereüntes autem
blasphemábant eum movéntes cápita sua, ^^ et dicéntes : Vah qui
déstruis templum Dei, et in triduo illud reædificas : salva temetipsum
: si Fílius Dei es, descénde de cruce. '! Similiter et principes
sacerdótum illudéntes cum scribis et senióribus dicébant : ** Alios
salvos fecit : seípsum non potest salvum fácere : si rex Israel est,
descéndat nunc de cruce, et crédimus ei : 45 confídit in Deo : líberet
nunc, si vult eum : dixit enim : Quia Filius Dei sum. ὁ’ Idipsum
autem et latrónes, qui crucifixi erant cum eo, int ei. 45 À sexta
autem hora ténebree facts sunt supér univérsam terram usque ad
horam nonam. 36 Et circa horam nonam clamávit Jesus voce magna,
dicens : Eli, Eli, gos sabactháni? hoc est : Deus meus, Deus meus, ut
quid dereliquisti me? 7 Quidam autem illic stantes, et audiéntes,
dicébant : Elíam vocat iste. ** Et erem currens unus ex eis accéptam
implévit acéto, et impósuit ΝΣ dabat ei bibere. 3% Céteri vero
dicébabi: Sine videámus an véniat. Elías liberans eum. 50 Jesus
autem iterum clamans voce magna, emísit spiritum. Ἢ Et ecce velum
templi scissum. est in duas partes a summo usque deórsum, et terra
mota est, et petræ scissæ sunt, ‫"ל‬‎et monuménta apérta sunt : et
multa. córpora sanctórum, qui dormíerant, surrexérunt, ?? et
exeüntes de monuméntis post resurrectiónem ejus, venérunt in
sanctam civitátem, et apparuérunt multis. *5 Centürio autem, et qui
cum eo erant, custodiéntes Jesum, viso terræmôtu et his quæ
fiébant, timuérunt valde, dicip 49. NBCX (e Jo.) ἄλλος δὲ λαβὼν
16γχην ἔννξεν αὐτοῦ τὴν πλευρὰν .‫א‬‎ἐξῆλϑεν ὕδωρ .‫א‬‎al c. 51. NT'*
ἀπὸ. BCT* ponit εἰς dvo post κάτω. 53, Αὐτοῦ (al. αὐτῶν) ex
explicatione? (pauci * »erá-ov1.). 54. BDLT®: τὰ yodp.
 | Matthieu, XXVII, 38-54. 139 Derniers jours (XXI-
XXWIHIE), — 3^ La Passion C XXVI, 36-XX VII).‫ווו‬. ‫‏‬sa
condamnation ainsi écrite : « Ce- 12 3X LUI-CI EST JÉSUS, LE ROI
DES JUIFS », Mare. 15, 26. 38 Alors furent crucifiés avec lui Mare.
15, 27. deux voleurs, l'un à droite et l'autre ‫ל‬‎à gauche. MNA TL ? Or
les passants le blasphé- mispnemaient, branlant la tête, *' et di- mis
s». sant : > Ah! toi qui détruis le temple 7*2 de Dieu et le rebâtis en
trois jours, go. 2, 19. sauve-toi toi-même. Si tu es le Fils πρὸ *': de
Dieu, descends de la croix ». 7% ** *! Pareillement les princes des
pré- s... 15, 51. tres eux-mêmes se moquant de lui 5575 7 avec les
scribes et les anciens, di- He». 5 9. saient : *? > Ila sauvé les
autres, {#5 et il ne peut se sauver lui-même : £&»*1* ‫ו‬‎. 1 4 > 5.
95, 10. s'il est le roi d'Israël, qu'il des- 3er. 25, 16. cende maintenant
de la croix, et nous croirons en lui: 7 il se confie 7«*'* en Dieu; qu'il
le délivre maintenant, ^ ' s'il veut; car il a dit : Je suis le Fils de Dieu
». ** Or, c'était aussi l'insulte que lui faisaient les voleurs qui étaient
crucifiés avec lui. 55 Mais, depuis la sixième heure, renebræ. H , :
Marc. 15, 33. les ténèbres se répandirent sur toute ri. 93, 4. la terre
jusqu'à la neuvième heure. $25 — 46 Et, vers la neuvième heure,
rrisio de Jésus cria d'une voix forte, disant : ,'5, > Eli, Eli, lamma
sabacthani? » c'est- Jos. 15 52. à-dire : « Mon Dieu, mon Dieu, pour
101 m' avez-vous délaissé? » 7 Mais quelques-uns de ceux qui xs: 1.
étaient là, et qui entendaient, disaient : > C'est Élie que celui-ci
appelle ». *5 Et aussitôt lun d'eux, 1e53e37. courant, prit une
éponge, l'emplit «s; 35. de vinaigre, puis la mit au bout d'un roseau,
et il lui présentait à boire. ^? Mais les autres disaient : « Laisse,
voyons si Elie viendra le délivrer ». ? Cependant Jésus, criant encore
woes Jesu. d'une voix forte, rendit l'esprit. Ts 5! Et voilà que le voile
du temple Portentase déchira en deux, depuis le haut rac 25,45. pro
bas, et la terre trembla, ui» 55: es pierres se fendirent, ?? les sé- »
9a $i Ps. 103, 32. pulcres s'ouvrirent, et beaucoup de ἘΝ Ὁ Act. 2.
29; corps des saints qui s'étaient en- δος 5. 39 dormis se leverent;
?? et sortant de xz» 5 14. leurs tombeaux, après sa résurrec- i ᾿ ,
tion, ils vinrent dans la cité sainte, 195 et apparurent à un grand
nombre de — personnes. . 54 Le centurion et ceux qui étaient
Centurioavec lui pour garder Jésus, voyant confessio. le tremblement
de terre et tout ce 5:36 qui se passait, furent saisis d'une $5
extréme frayeur, et dirent : « VraiMarc. 15, 32. Luc. 23, 39. Is. 26,
18. elles devaient être très visibles à la hauteur où Ponce Pilate les
fit placer. Les mots sont écrils [au rebours] de droite à gauche, en
suivant l'ordre du titre hébreu, et les lettres sont renver- , sées,
comme si on les voyait dans une glace ». (Rohault de Fleury). Le
titre de la croix, dans son intégrité, devait avoir approximativement
65 centimetres sur 20. 39-44. Insultes au Sauveur. Comparer avec
Marc, Xv, 29-32; Luc, xxii, 35-39. 40. Le temple, en grec ναός. Voir
plus haut la note sur xxi, 12. 44. Saint Luc ne parle que d'un seul
voleur qui ait insulté Jésus-Christ; mais on peut trés légitimement
supposer que les deux voleurs s'étaient d'abord permis ces insultes,
et qu'ensuite l'un d'eux, touché de la gràce, blàma l'insolence de son
compagnon. On est encore fondé à dire que saint Matthieu parle
ainsi de ces voleurs indistinctement, et qu'il a mis le pluriel pour le
singulier, genre de licence qui se rencontre quelquefois dans les
écrivains sacrés (Glaire). 45-53. Ténèbres et autres prodiges.
Comparer avec Marc. xv. 93-38; Luc, xxii, 44-45. 1 45. Depuis la
siriéme heure..; depuis midi jusqu'à trois heures. — Toute la terre,
signifie, selon plusieurs, la Judée et quelques pays voisins. 46. Eli,
Eli... Ce sont les premieres paroles du Psaume xxi, qui prédit la
passion. Notre-Seigneur s'exprime en syro-chaldéen ou araméen, qui
était la langue alors usitée en Palestine. 50. Jésus... rendit l'esprit.
Cétait le vendredi 14 nisan, à trois heures de l'aprés-midi, c'està-
dire, selon les calculs les plus probables, le vendredi 7 avril de l'an
30 de notre ere. 51. Le voile du temple, en grec vais. Il y avait dans
le temple de Jérusalem deux voiles ou portiéres. Le premier voile
séparait le portique du Saint; le second séparait le Saint du Saint des
Saints. C'est ce dernier qui fut déchiré en deux au moment dela mort
de Notre-Seigneur. 32. Qui s'étaient endormis; c'est-à-dire qui
étaient morts. Souvent dans lÉcriture le sommeil est mis pour la
mort. 54-56. Centurion et autres spectateurs. Comparer avec Marc,
xv, 39-41 ; Jean, XXII, 41-49. 54. Le centurion et ceux qui étaient
avec lui pour garder Jésus. « Les corps étaient gardés. Pétrone, dans
une satire, dit que les soldats veillaient pour qu'on ne les dérobât
pas pour les ensevelir. Il ajoute que les parents d'un crucifié
profiterent d'une nuit oü les soldats étaient absents et enlevérent le
corps de la croix ». (Rohault de Fleury).
 140 Matthæus, XXVII, 55-63. Ultima Jesu ( XXI-XXWIII. —
# Passio Christi (XX VI, 36-XX VID).‫וון‬. ‫‏‬yovttg ᾿“ληθῶς ϑεοῖ υἱὸς ἣν
οὗτος. ὅδ σαν δὲ ἐχεῖ γυναῖχες πολλαὶ ὠπὸ αχούϑεν ϑεωοοῦσαι,
αἵτινες ἠκολούϑησαν paxoo 0 7 τῶ ᾿Ιησοῦ ἀπὸ τῆς Γαλιλαίας
διακονοῦσαι La , *‫כ‬. 362 2 * , ‫‏‬αὐτῷ" δ ἐν αἷς ἦν Μαρία ἡ
“Μαγδαληνή, καὶ‫‏‬Μαρία ἡ τοῦ ᾿Ιακώβου καὶ Ἰωσῆ μήτηρ, καὶ‫‏‬μήτηρ
τῶν υἱῶν Ζεβεδαίου.5 ‫‏‬ὅτ Οψίας δὲ γενομένης, ἦλϑεν ἄνθϑρω, , ^ ‫כ‬‎
, » πος πλούσιος ἀπο 4 τοὔνομα Ἰωσήφ, ὃς καὶ αὐτὸς ἐμαϑήτευσε
τῷ 1% σοῦ. 6% ‫ה‬‎0006/00 τῷ Πιλάτῳ ἠτήσατο τὸ σῶμα τοῦ Ἰησοῖ.
Τύτε 0 Tlüëτος ἐχέλευσεν ἀποδοϑῆναι τὸ σῶμα. 59 Kai * ^ - 6 ? ^ ‫כ‬‎
, 2 * λαβὼν τὸ σῶμα 0 Toon ἐνετύλιξεν αὐτὸ σινδόνι καϑαρᾷ, xai
ἔϑηκεν αὐτὸ ἐν τῷ καινῷ αὑτοῦ μνημείῳ, ὃ ἐλατόμησεν ἐν τῇ πέτρᾳ,
καὶ προςκυλίσας λίϑον μέγαν τῇ , - , ) « 617 ^ ϑύρᾳ τοῦ μνημείου
ἀπῆλθεν. 2 Hv δὲ ἐχεῖ Mala ἡ “Παγδαληνὴ xoi ἡ ἄλλη Mapia,
καϑήμεναι ἀπέναντι τοῦ τάφου. Ty δὲ ἐπαίριον, ἥτις ἐστὶ μετὰ τὴν
παρασκευήν, συνήχϑησαν ot ἀρχιερεῖς xai οἱ Φαρισαῖοι πρὸς
Πιλᾶτον, "5 λέγοντες" Κύριε, ἐμνήσθημεν ὅτι ἐκεῖνος ὃ πλάνος εἶπεν
ἔτι ζῶν" Μετὰ τρεῖς ἡμέρας ἐγείρομαι. céntes : Vere Filius Dei erat
iste. % Erant autem ibi mulíeres multe a longe, quæ secütæ erant
Jesum a Galiléa, = ministrántes ei : ** inter quas erat María |
Magdaléne, et María Jacóbi, et Joseph ed mater, et mater filiórum
Zebed#i,. 97 Cum autem sero factum esset, venit quidam homo
dives ab Arimath#a, nómine Joseph, qui et ipse discípulus erat Jesu
: ὅδ hie accéssit ad Pilátum, et pétiit corpus Jesu. Tune Pilátus jussit
reddi corpus. ?? Et accépto córpore, Joseph invólvit illud in síndone
munda. ** Et pósuit illud in monuménto suo novo, quod excíderat in
petra. Et advólvit saxum magnum ad óstium monuménti, et ábiit. 6!
Erat autem ibi María Magdaléne, et ältera María, sedéntes contra 9
chrum. | 53 Altera autem die, quæ est post Parascéven, convenérunt
principes sacerdótum et pharis#i ad Pilátum, ** dicéntes : Dómine,
recordáti sumus, quia sedüctor ille dixit adhuc vivens : Post
Résurrection (XXY III, 6, p. 143). (Ampoule de Jérusalem donnée à
la reine Théodelinde par le pape salut Grégoire). 56. C: Μαριὰμ.
NDT*: Ἰωσὴφ. 57. NCDLT*; ἐμαϑητεύϑη. 88. NBT?* a ) τὸ σῶμα.
59. BDT! + ἐν $0. A Joseph, membre du sanhédrin, Mare, xv, 43;‫‏‬
‫דט‬. homme bon et juste, Luc, xxu, 50. D'après une tra-‫‏‬dition,
Joseph fut un des soixante-douze disciples,‫‏‬et il aurait porté la foi en
Grande-Bretagne.60 ‫‏‬, It roula... Cette expression est vraie à la lettre.
L'antique tombeau dit des Rois, prés de Jérusalem, se ferme au
moyen d'une pierre qui est ronde comme une meule de moulin et
qui se roule devant lentrée. Pour ouvrir, on roule la pierre en sens
opposé dans une sorte de rainure destinée à la recevoir.
 | Matthieu, XXVII, 55-63. 141 Derniers jours (XXI-XX WII).
— 3 La Passion C XXVI, 36- XXVII).‫זוו‬. ‫‏‬ment, celui-ci était le. Fils de
Dieu ». ! 7** 5 39. 55 Il y avait aussi à quelque dis- ,aexante-tance
de là beaucoup de femmes sis qui, de la Galilée, avaient suivi Jésus ,
5,7. ur le servir; 5% 6% parmi lesquelles 150% étaient Marie
Madeleine, et Marie, τς ur mère de Jacques et de Joseph, et la 30,
30: 36, 7. mère des fils de Zébédée. 57 Or, d il se fit soir, vint un
Seveliter homme riche d'Arimathie, du nom mare. 15, 43. de Joseph,
qui lui aussi était dis- Jon 19, 38. ciple de Jésus. ** Cet homme vint
à «2*7 Pilate, et lui demanda le corps de 3.15; Jésus. Alors Pilate
commanda que "^^^ le corps fût remis. * Ayant donc recu le corps,
Joseph l'enveloppa dans un linceul blanc; °° et il le mit 5 7 *. dans
son sépulcre neuf qu'il avait i fait tailler dans le roc. Ensuite il roula
une grande pierre à l'entrée du sépulere, et s'en alla. δ' Mais
MarieMadeleine et l'autre Marie étaient là, z«. 19, 14. assises prés
du sépulcre. 65 Le lendemain, c'est-à-dire le Custoaï je d’après la
préparation du sab- pulchrum. at, les princes des prêtres et les
harisiens vinrent ensemble vers Piate, 5 et lui dirent : > Seigneur,
nous nous sommes rappelé que ce séducteur a dit, lorsqu'il vivait
encore : Aprés trois jours je ressusciLuc. 23, 55. 56. « Marie-
Madeleine est célébre dans l'Évangile par ses sentiments de charité
ardente envers le Sauveur des hommes, et dans la tradition
ecclésiastique par ses larmes et sa pénitence. Le surnom de
Madeleine fut donné à Marie, parce qu'elle était du bourg de
Magdala, en Galilée, pres du lac de Tibériade. On croit qu'elle était
d’une famille distinguée par ses richesses. L'Évangile, en la nommant
pécheresse, a fait supposer qu'elle s'était abandonnée à des
débordements. On connait le châtiment que Marie-Madeleine subit
durant quelques années: elle fut tourmentée du démon jusqu'au jour
où le Sauveur, lui remettant ses péchés, l’affranchit de cette
domination horrible. [Quand elle versa ses parfums sur les pieds de
Jésus, il lui remit ses péchés]. C'est depuis cette époque qu'elle
s'imposa des pratiques de pénitence. Aprés avoir mis sa chevelure et
ses parfums aux pieds du Seigneur, comme si elle avait voulu figurer
son renoncement à toutes choses vaines, elle se joignit à quelques
saintes et nobles femmes qui suivaient le divin Maitre, écoutaient ses
prédications et l'assistaient de leurs biens dans ses courses
évangéliques. MarieMadeleine et les saintes femmes suivirent Jésus
de la Galilée à Jérusalem et elles ne l'abandonnerent pas, méme à
sa mort, qui arriva six mois aprés. Marie avec sa famille habitait le
bourg de Béthanie. [C'est là que mourut son frere Lazare, et c'est là
que Jésus le ressuscita. Peu aprés, dans un repas qui fut donné à
Béthanie au Sauveur chez un homme qui avait été guéri de la lèpre
et où Lazare assistail avec ses deux sœurs, Marie répandit un
nouveau vase de parfums sur les pieds du Sauveur]. Malgré les
souffrances de son amour, Madeleine accompagna Jésus sur le
Calvaire. [Elle lui renditles derniers devoirs de la sépulture et mérita
de voir des premieres son Maitre ressuscité]. A partir de cet instant,
on ne trouve plus dans l'Évangile aucune trace de sainte Madeleine.
11 est probable toutefois qu'elle se rendit d'abord en Galilée, où
Jésus devait se manifester à ses disciples. Ce fut l'opinion générale
des anciens que, apres la descente du Saint-Esprit et la dispersion
des Apótres, Marie-Madeleine quitta Jérusalem et la Palestine. La
tradition [la] plus fondée fait aborder Marie-Madeleine en Provence
avec Marthe et Lazare. D’après cette tradition, Lazare devint évêque
de Marseille où il mourut: Marthe porta l'Évangile à Tarascon, et
Marie-Madeleine se retira dans la caverne devenue si célèbre sous le
nom de Sainte-Baume. C'est là qu'elle finit ses jours dans les
pratiques de la pénitence ». (M** Darboy). — Marie, mère de
Jacques et de Joseph, femme de Cléophas ou Alphée, sœur ou belle-
sœur de la sainte Vierge, mère de saint Jacques le Mineur. — Sur
Jacques et Joseph, ou Josés, voir plus haut la note de xir, 55, 56. —
La mér e des fils de Zébédée, Salomé, mére de saint Jacques le
Majeur et de saint Jean l'Évangéliste. 51-61. Sépulture. Comparer
avec Marc, xv, 42-47; Luc, xxim, 50-55; Jean, xix, 38-42. : ὅτ.
Arimathie, d’après Eusèbe, est la Ramathaim-Sophim située dans les
montagnes d'Ephraim, non loin de Béthel. D'après saint/Jéróme,
c’est la Ramléh actuelle, à quelques kilomètres de Lydda. 58. Les lois
romaines défendaient de donner la sépulture aux criminels sans la
permission des juges. — > La croix était le tombeau du supplicié.
Les Juifs attachèrent ques à la croix les cadavres des sup6 liciés,
mais ils ne les y abandonnaient jamais après le cou er du soleil. Les
Romains, plus cruels, y E ent les condamnés vivants et les laissaient
périr misérablement de faim, de soif et d'épuisement. Leurs corps
devenaient la proie des vautours et des chiens et se détruisaient en
général par la putréfaction ». (Rohault de Fleury). 59. Joseph
l'enveloppa dans un linceul blanc. « Le suaire dont se servit Joseph
d'Arimathie devait enPopper décemment le corps pour le porter au
tombeau, indépendamment des autres linges nécessaires à Tem
umement > dont parle saint Jean, xix, 40; xx, 5, 7. (Rohault de
Fleury). On honore à Cadouin (Dordogne) et à Turin le saint suaire
de Notre-Seigneur. « La longueur du saint suaire [de Cadouin] est de
2 m. 81; sa largeur de m. 13. La pièce d'étoffe est entière, ayant
une lisière sur les deux côtés larges et une bordure coloriée sur les
deux cótés longs ». (De Gourgues). Quant au saint suaire de Turin, «
c'est une pièce d'étoffe de quatre mètres environ de longueur, en lin,
un peu jauni par le temps et rayé comme du basin. [On y voit
représenté le corps de Notre-Seigneur]. Le temps a fait dans le tissu
des trous imperceptibles dont quelques-uns ont été réparés par les
princesses [de Savoie] ». (M** Jeancart). 60. C'était la coutume
dans ce pays de faire tailler dans le roc des tombeaux pour les
personnes de considération. — Dans son sépulcre. D’après la
tradition, le tombeau de Joseph d'Arimathie était composé de deux
chambres, taillées l'une et l'autre dans le roc, et dont la première
servait de vestibule à la seconde où avait été déposé le corps du
Sauveur. Sainte Hélène, en préparant le terrain pour isoler le
tombeau de Notre-Seigneur, placé aujourd'hui au milieu de la
rotonde de l'église du Saint-Sépulcre, moditia la forme du monument
et le rendit quadrangulaire. La premiere chambre du tombeau,
nommée chapelle de l'ange, parce qu'on eroit que c'est là que l'Ange
annonca aux saintes femmes la résurrection du Sauveur, est une
sorte de vestibule long de 3 m. 45 sur 2 m. 90 de large. On entre
par une petite porte très basse percée dans le mur ouest dans la
seconde chambre appelée chapelle du tombeau de Notre-Seigneur.
Elle a 2 m. ΟἹ de Tong sur 4 m. 93 de large. etd ee a de marbre
blanc couvrent le roc naturel. Le tombeau proprement dit s'élève de
65 centimètres au-dessus du pavement; il est long de 1 mètre 89 et
large de 93 centimètres. Il est creusé en forme d'auge et adhérent
aux parois ouest-nord et est. — I| roula une grande pierre. Les
tombeaux. étant des grottes ou des édifices, sont fermés par une
porte ou par une pierre. 62-66. Garde du sépulcre. Propre à saint
Matthieu. — . 62. Le jour d’après la préparation du sabbat: c’est-à-
dire le jour méme du sabbat. Les Juifs appelaient le vendredi la
préparation du sabbat, parce qu'on y préparait à manger, ce qu'il
n'était pas permis de
 142 Matthæus, XXVII, 64 —XXVIII, 13. Ultima Jesu (XVXI-
XXWIII). — 4" Glorificatio Christi ) XXVII).‫ווו‬. ‫‏‬δὲ Κέλευσον οὖν
ὠσφαλισϑῆναι τὸν τάφον ἕως τῆς τρίτης ἡμέρας, μήποτε ἐλθόντες οἱ
μαϑηταὶ αὐτοῦ νυχτὸς κλέψωσιν αὐτὸν καὶ εἴπωσι τῷ λαῷ" "Hyég9m
ὑπὸ τῶν νε- Av e , “χρῶν, καὶ ἔσται η ἐσχάτη πλάνη V ν τῆς πρώτης.
""Eqn δὲ αὐτοῖς ὁ Πιλᾶτος. Ἔχετε κουστωδίαν" ὑπάγετε,
ἀσφαλίσασϑε Piu « ^ , ὡς οἴδατε. δ᾽ Où δὲ πορευϑέντες ἠσφαλίM , ,
carro τὸν τάφον, σφραγίσαντες τὸν λίϑον μετὰ τῆς κουστωδίας. ^
.‫ווגצטאא‬‎'Oy? δὲ σαββάτων, τῇ èm, » , , , φωσκούσῃ sic μίαν
σαββάτων, 1495 Maola ἡ MaydaAnvi xal ἡ ἄλλη Mato ϑεωρῆσαι ^ , 2
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κυρίου καταβὰς ἐξ οὐραγοῦ, προςελϑὼν ἀπεχύλισε τὸν λίϑον ἀπὸ τῆς
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