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CHEMISTRY OF FUNCTIONAL MATERIALS
SURFACES AND INTERFACES
CHEMISTRY OF
FUNCTIONAL
MATERIALS
SURFACES AND
INTERFACES
Fundamentals and Applications

ANDREI HONCIUC
Elsevier
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 Preface
In these times it is undeniable that most industries deal
increasingly more often than ever with surface and inter-
facial phenomena. Chemists, physicists, and material sci-
entists, with background and training in materials,
surfaces, and interfaces are in great demand. From my
experience in both industry and academia, I have
observed that students attending courses of a general
chemistry degree program encounter rather late in their
curriculum courses dealing with interfacial phenomena
and chemistry of interfaces. Some curricula have
included the chemistry of interfaces under different for-
mats, at the undergraduate level, some only at master’s
level, in specialized modules. This can in part be
explained by the fact that Chemistry has become an enor-
mously vast array of scientific domains, branching into
biochemistry, organic chemistry, physical chemistry,
catalysis, industrial chemistry, inorganic chemistry, ana-
lytical chemistry, materials chemistry, nanotechnology,
polymer chemistry, petroleum chemistry, etc. Due to
fecund research in the past two decades Chemistry of
functional materials and interfaces covers a multitude
of intertwined interdisciplinary subjects from the nano-
scale, such as synthesis of polymeric and inorganic nano-
particles, to macroscopic phenomena such as
manufacturing of functional surfaces, food, and con-
sumer products such as cosmetics, detergents, heteroge-
neous catalysts, etc. The amplitude and the amount of
information in each of these fields put pressure on stu-
dents, more so than several decades ago; it is now harder
for the students to keep track of the newest advances,
vii
even less so acquire a relevant practical experience. Nav-
igating through the maze of scientific literature and infor-
mation hard to decipher can be extremely intimidating
for the future chemists. The same is true in industry;
working in industry one realizes that time is of the
essence. Chemists and laboratory technicians are
expected by the company to be innovative and thrive
in interdisciplinary fields, learn on the go, and become
experts in the shortest amount of time, on the job. There-
fore, I feel that this book would be useful as a textbook for
students, chemists working in industry, and laboratory
technicians first encountering the chemistry of interfaces,
interfacial phenomena, colloids, nanotechnology, poly-
mer nanoparticle synthesis, etc. I have used myself part
of this material in my teachings both in academia and
training of technicians from industry. While this material
used as a coursework material at master’s level has ini-
tially included much more theory and formula, I could
feel the students had difficulties grasping these, due to
the pressure, lack of time, and an extremely burdening
curriculum. I thus preferred to make the hard choice of
reducing the material only to essential theories and adopt
a more descriptive and intuitive presentation. One of the
leitmotifs of the book is the emphasis on practical appli-
cations of such theories. After several years in refining
this material I believe it came to a format well received
by the students. In addition, to make it more useful for
chemists performing interfacial experiments, in industry
or academia, I have tried to add experimental details or
hints on data interpretation from my own experience.
 C H A P T E R

1
Introduction

Interfaces are the boundaries separating two phases and define all objects in the three-dimensional world. Depend-
ing on the strength of cohesion forces and binding energies between atoms and molecules, the phases can be gases,
liquids, and solids, defining the physical states of matter. When the cohesion energies between the constituting atoms
and molecules are stronger than randomizing effects of the thermal energy, the physical state changes from gas to a
condensed phase of matter, liquid, or solid. The Boltzmann distribution gives the probability P that a system will be in
a certain state as a function of the state’s energy and temperature:
P
eE=kT
kT factor is often used as a scale energy factor in the molecular interactions. The cohesive energies per atom or molecule
at 298 K can vary from several kT between gas atoms, between
9 and
23 kT in liquid Hg (the liquid with the strongest
cohesive energy, 57.9 kJ/mol [1]), and >50 kT in solids up to 342 kT in W (1 kT  4.05  1021 J), the metal with the high-
est melting point. The kT energy scale factor is introduced and discussed in detail in Chapter 2. Because the most
important interactions between material interfaces take place in the liquid, or between material interfaces and liquids,
the solid-liquid, liquid-liquid, and liquid-air interfaces deserve special attention. The overall balance between the
repulsive and attractive forces between solutes and colloidal objects in liquids must be comparatively equal or larger
than 9–23 kT to have aggregation, adsorption, self-assembly, etc., and below 9 kT to obtain stable dispersions and col-
loids. As mentioned, liquids form at T ¼ 298 K, when the cohesive energy between the constituting atoms and mole-
cules is larger than 9 kT. While in the bulk of a liquid the interaction forces of a molecule or atom are fully symmetric at
interfaces, in contrast, in the topmost layer of molecules or atoms the interaction forces are asymmetric. Due to this
asymmetry, a certain tension/force arises in the plane of the interface. The stronger the interfacial tension, the stronger
the asymmetry. At contact between two phases, the topmost layer of molecules at the phase boundary also interacts
with the molecules from the other phase, this is called adhesion. The adhesion forces and energies counterbalance the
asymmetry of the forces acting on the topmost molecular layer, i.e., the stronger the adhesion force, the smaller the
interfacial tension. If the adhesion force is stronger than the cohesion force, then the interfacial tension disappears,
the interface disappears, and the phases become fully miscible, as discussed in Chapter 3. This interfacial tension
has also the character of an energy density, and for pristine interfaces this is causally related to the cohesion energy
in the bulk material; interfacial energy density is about half the cohesion energy in bulk. Surface and interfacial tension
of liquid-gas and liquid interfaces, as well as interfacial and surface energy of solids-liquid and solid-gas interfaces, are
thoroughly discussed in Chapter 3. The effects of the interface tension can be seen in small liquid droplets or molten
metals, as the shape of the droplet itself is modeled by this interfacial tension. The small world of insects and bugs are
particularly affected by the interfacial tension. Because their size is comparable to the capillary length, when the shape
of the liquids is fully determined by interfacial tension, not by gravitation, they have a different perception of the sur-
rounding world than humans do. Interfacial tension can have a devastating effect on insects; some drown as they can-
not escape the surface tension, but some have adapted to take full advantage of it. For example, small water droplets
can be manipulated and transported by ants without any need for bottles or glasses, and some mosquitos have adapted
on water to straddle along the smooth water surface, etc. (Fig. 1).
Intuitively, the interfacial tension is the 2D equivalent of the cohesion energy in 3D. Interfacial tension is discussed in
detail in Chapter 3.
However, when the surface and the interface are chemically modified, e.g., with surfactant adsorbates, the inter-
facial tension and energy density of interfaces do not reflect anymore the cohesive energy between the molecules
in the bulk phase. Thus, the interface itself can be treated as a thermodynamic system on its own, as discussed in
Chapter 7. The interfacial tension and interfacial energy density between phases are now an exclusive reflection of

Chemistry of Functional Materials Surfaces and Interfaces 1 Copyright © 2021 Elsevier Inc. All rights reserved.
https://doi.org/10.1016/B978-0-12-821059-8.00004-1
2 1. Introduction

FIG. 1 (A) Ant drinking water (https://www.shutterstock.com/image-photo/ant-drinking-water-505718482); (B) mosquito striding on the sur-
face of water (https://www.shutterstock.com/image-photo/water-bug-standing-on-surface-calm-1732352752).

the lateral interactions between surfactant molecules, polymers, or particles adsorbed at the interface. In fact, under-
standing how to change the interfacial tension and energy density between phases was one of the key enabling ele-
ments in the development of most technological advances in the 20th and 21st centuries, ranging from detergency, oil,
and ore extraction to the advanced manufacturing of processors and advanced electronic devices (see Chapter 15).
Surfactants and amphiphiles are molecules, polymers, and other building blocks of matter that adsorb spontane-
ously at interfaces. Surfactants lower the interfacial tension and energy density between phases (water-oil, water-gas,
solid-water) independently of their cohesion energy. This enables the formation of emulsions and foams and increase
in surface wettability. Earlier, it was mentioned that when the adhesion forces are stronger than the cohesion forces
between two liquids, the interfacial tension vanishes, and the liquids become miscible. The fact that, in the presence of a
surfactant at interfaces, the interfacial tension is not anymore a true reflection of the bulk cohesion energy of the phases
can be understood from the following example. If the interfacial tension between two water and oil phases becomes
vanishingly small due to the addition of a surfactant, then the two phases do not mix, but this time they form emulsions
consisting of very fine oil droplets dispersed into water. Chapter 4 gives an introduction into the vast field of surfactant
chemistry. Emphasis is given on surfactant classification, surfactant design, and structure activity relationship. In sim-
ple words, what makes a surfactant effective and how is this reflected in different physicochemical parameters?
Chapter 4 also introduces other amphiphiles, such as Janus nanoparticles and supra-amphiphiles, noting that amphi-
philicity is a scalable property, being active well beyond the molecular scale, well into the nano- and microscales.
Amphiphiles and surfactants have an important property, which is to self-assemble into suprastructures. This enables
the creation of smart, reconfigurable, or “environmentally aware” materials, bottom up, via self-assembly processes.
Most of the surfaces we interact with on a daily basis are solid, such as the screen of the smartphone, the cup of
coffee, the wheel of the car, etc. The tactile feel, the adhesion, is determined by the interfacial energy between our skin
and these surfaces. In the modern world, the concept of functional surfaces is gaining more popularity and it becomes a
requirement in the consumer products. Functional surfaces can be defined as surfaces that perform a function, such as
self-cleaning windows, or have a superior property, such as antiadherent, omniphobic antifingerprint in smartphone
screens, for example, while others are icephobic, or antifogging, etc. The key concepts in understanding the phenom-
ena behind functional surfaces and interfaces are adhesion and wetting. Surface wetting refers mainly to the interaction
of a liquid with a solid surface. Earlier, it was mentioned that when the adhesion forces are stronger than the cohesion
forces between two liquids, the interfacial tension vanishes, and the liquids become miscible. The interfacial tension or
energy between a solid and a liquid can also be altered, for example, with surfactants; however, when the interfacial
energy between a solid and a liquid becomes vanishingly small, the solid surface becomes fully wetted by the liquid.
The converse is true: when the interfacial energy is large, the surface becomes nonwetted, and the liquid pearls up on
the surface of the solid. Scientists have learned that, in addition to interfacial energy between the solid and liquid, the
geometry of the interface is key to designing functional surfaces. Finding inspiration in nature, scientists found out that
hierarchical structuring of the surface of the solid can lead to a variety of functional surfaces, such as superhydropho-
bic, superhydrophilic, icephobic, omniphobic, self-cleaning, etc. Chapter 5 gives an overview of the phenomena of
 Reference 3
wetting, wettability, and contact angle as the main measurement methods for macroscopic and nanoscale surfaces.
Chapter 5 also introduces the several functional surfaces.
In Chapter 6, a series of equations permitting the calculation of unknown surface tension, energy, work of adhesion,
etc. from known measurable macroscopic parameters have been grouped under the name “fundamental equation of
interfaces.” Their versatility in predicting the values of many interfacial parameters, for example, interfacial tension,
wettability, polarity of the surface, etc. from contact angle makes them extremely useful in practice. In Chapter 7, the
surface and interfacial tension are introduced via thermodynamic treatment of the interfacial layer. Although this
treatment has no direct practical implications, it gives the theoretical background necessary for the interpretation
of interfacial adsorption isotherms and interfacial tension vs concentration curves for surfactants and amphiphiles.
Chapter 8 treats surface functionalization that can be achieved in different ways, by physical methods such as
roughening of the surface, or photolithographic nanopatterning, and by chemical methods, by adsorption of surfactant
molecules. The adsorption of surfactant molecules on solid surfaces involves either chemical or physical bonding,
resulting in the formation of a self-assembled monolayer. Several types of chemical bonding and substrates are
reviewed. In addition, a surfactant monolayer can be prepared first at the water-air interface and then transferred onto
the surface of the solid via the Langmuir-Blodgett and dip-coating methods.
Solid-solid interfaces also have practical relevance, especially in layered electronic devices. Solid-solid interface, in
particular the metal-organic interface, is the locus of another type of phenomena of practical importance, namely the
electron transfer. In the previous chapters, the interfaces were the place where different forces met. In Chapter 9, the
metal-organic interfaces are treated as the contact point between electron energy levels of a metal, material with delo-
calized electron energy levels called bands, and the organic molecules and polymers whose energy levels are discrete
and localized. Understanding electron transfer between metal electrodes and organic conductors is of practical impor-
tance, especially for the manufacturing of organic photovoltaics, organic light emitting diodes, and other organic elec-
tronic devices. Any of these devices requires at least several layers of electroactive organic materials, and knowledge of
adhesion, wettability, and interfaces is required for their development and manufacturing.
Chapters 10 and 11 deal with the interaction forces and energies between interfaces in different media. These inter-
action forces can be repulsive or attractive and they are the same forces governing the molecular interactions. The bal-
ance between the attractive and repulsive interaction forces is of practical importance, controlling the phenomena of
particle aggregation, colloid stability, particle adsorption on surfaces, self-assembly of nanoparticles, etc. Chapter 12
introduces colloids, which are the oldest type of nanomaterials known and are today encountered in the food industry,
pharma, and many other consumer products. Colloids are constituted from finely divided particles, nanoparticles, or
liquid droplets dispersed into a continuous medium. Because their surface-to-volume ratio is very high, their behavior
is governed almost exclusively by their surface and interfacial properties. Synthesis of colloids as well as stability cri-
teria is discussed.
As a continuation on the topic of colloids, but deserving special attention, Chapter 13 introduces the synthesis of
polymeric nanoparticles and polymeric nanostructured interfaces via emulsion polymerizations. As expected, the
interfacial aspects determine the types of emulsions and nature of the nanomaterials that can be synthesized. The types
of emulsions and conditions of formation are briefly reviewed. A case study covers some examples of synthesis of
nanostructured interfaces, polymerization of the emulsions stabilized by amphiphilic particles.
Some nanoparticles, depending on their surface properties, can also spontaneously adsorb at interfaces; they can
form monolayers and stabilize emulsions. The factors responsible for why some particles can adsorb at liquid-liquid,
liquid-gas, and solid-liquid interfaces are discussed in Chapter 14. Once adsorbed at the interfaces the particle-particle
interactions leads to the decrease in the interfacial tension. Responsible for this is their lateral interaction, which is
governed by the same types of forces as in case surfactants, and in addition by particle specific interactions, capillary
floatation, or immersion forces. In fact, in recent times, nanoparticles have been used in the synthesis of photonic crys-
tals via the Langmuir-Blodgett method and other self-assembly structures.
The last chapter of this book discusses the role of interfaces in integrated circuit manufacturing via photolithogra-
phy. Photolithography is the only top-down preparation method of nanomaterials and nanostructured surfaces. In the
past few years, it evolved into the most precise technique to prepare with large machines, structures as small as 7 nm
(the gate of the field-effect transistor). In practice, the photolithographic manufacturing process of chips and processors
requires in-depth knowledge and control of interfacial phenomena such as adhesion, wetting, capillary forces, and
interfaces.

Reference
[1] G. Kaptay, G. Csicsovszki, M.S. Yaghmaee, An absolute scale for the cohesion energy of pure metals, Mater. Sci. Forum. 414–415 (2003) 235–240.
https://doi.org/10.4028/www.scientific.net/MSF.414-415.235.
 C H A P T E R

2
Thermal energy scale kT

At the nanoscale, the interaction energies are generally expressed in multiples of kT, also referred to as the thermal
energy scale. The average kinetic energy of a gas atom with three degrees of freedom is 3/2 kT, is roughly the energy of
thermal fluctuations at a given temperature
1 kT. The thermal energy has a randomizing effect contributing to an
increase in the entropy of the thermodynamic system. By expressing the energy of intermolecular interactions or nano-
particle interactions as multiples of kT, the interaction strength can be compared with the randomizing effect of
temperature.
Next, it is instructive to follow the kT in several different contexts as well as its origin. A thermodynamic system will
tend to move toward a lower energy state when available. When applied to chemical systems, for example, a solute in
a solution or a gas has a chemical potential defined as the rate of change of the Gibbs free energy with the number of
species in the system, at constant temperature and pressure:


δG
μi ¼ (2.1)
δNi T, P
Therefore, the change in chemical potential of a gas or a solute in a solution changes with the change in concentration.
Chemical potentials are important in describing the equilibrium in physicochemical processes such as evaporation,
melting, boiling, solubility, interfacial adsorption, liquid-liquid extraction, etc. The reason why the chemical potentials
are so important in the equilibrium chemistry is that when the two chemical systems are open and can exchange mol-
ecules or atoms, the rate of change of their free energy would be equal when equilibrium is established. Take, for exam-
ple, the molecules in the vapor and the liquid phase at equilibrium; by equating the chemical potentials of the molecule
of type i in two phases at equilibrium, or two regions 1 and 2, we obtain
μ1i + kT ln Xi1 ¼ μ2i + kT ln Xi2 (2.2)
At equilibrium between n different phases, the above equality must be satisfied for all phases:
μni + kT ln Xin ¼ constant (2.3)
where Xni
is the molecular fraction, volume fraction, or concentration of solute in phase n. For pure solution, this is
usually taken as unity. The factor k ln X is known under different names, such as the entropy of mixing, configuration
entropy, entropy of confining the molecules, etc.
Eq. (2.2) gives us the possibility to calculate the distribution of molecules between two phases, or two regions of
space at equilibrium, for example, a liquid in equilibrium with its vapors, or the distribution of the molecules of
gas in the atmosphere due to changes in the gravitational potential with altitude. For example, the number density
ρz of the molecules of gas in the Earth’s atmosphere changes with the altitude z and the mathematical function that
gives us the possibility to predict this change is
μzi + kT ln ρzi ¼ μ0i + kT ln ρ0i (2.4)
where ρzi is the number density of molecule i at altitude z and ρ0i is the number density of molecules of gas i at the
surface of the Earth z ¼ 0. Rearranging the above formula gives us the barometric formula or barometric law that gives
the density at the altitude z as a function of the number density of air molecules at the sea level ρ0i :

Chemistry of Functional Materials Surfaces and Interfaces 5 Copyright © 2021 Elsevier Inc. All rights reserved.
https://doi.org/10.1016/B978-0-12-821059-8.00015-6
6 2. Thermal energy scale kT

 z 

 μi  μ0i ðmgzÞ
ρzi ¼ ρ0i exp ¼ ρi exp
0
(2.5)
kT kT
where m is the molecular mass and g is the gravitational acceleration. Note that the potential energy of the air mol-
ecules mgz is “compared” to the kT at any height above the Earth’s surface. With the increase in the potential energy of
the molecules compared to kT, less molecules are found at higher altitudes (Fig. 2.1). In other words, if mgz is small
compared to kT, then the thermal energy would uniformize the distribution of molecules with the altitude such that
little variation in the number density of air molecules would be registered.
The same distribution applies to ions that, for example, carry a charge e between two different regions that have
different potentials ψ 1 and ψ 2:


eðψ 2  ψ 1 Þ
ρ2i ¼ ρ1i exp (2.6)
kT
and this is known as the Nernst equation. It is nonetheless important to note that interactions are additive; for example,
if the difference in energy between two regions is given by potential, potential energy, and chemical potential, then the
exponent will be the sum of all these contributions.
The above equations also give us the possibility to gauge the strength of interaction between molecules. For exam-
ple, if a liquid is in equilibrium with its vapors at standard conditions of pressure 1 atm and temperature 298 K, then
1 mol of gas will occupy approximately 22.4 m3 and a mole of liquid approximately 0.02 m3. Then the difference in
energy between the liquid and gas states will be [1]:
gas
0 gas 0 liquid Xi 22:4
μi  μi
kT ln liq

kT ln
7kT (2.7)
Xi 0:02

where 1 kT is approximately the energy of the thermal fluctuations. Therefore, it can be said that if the interaction
strength between molecules in a gas phase at temperature T is larger than 7 kT, then it condenses into liquid. Con-
versely, if the cohesion strength between the molecules of a liquid become smaller than 7 kT, then it transforms into
gas as the cohesion energy is simply too low to hold the molecules together. This alludes to what is known as the
Trouton rule, which states that the entropy of vaporization is roughly the same for different kinds of liquids, about
85 J K1 mol1, which is roughly 9.5 kT.

FIG. 2.1 The bottle was capped (left) in the mountain and brought to the ground level (right).
 2. Thermal energy scale kT 7

FIG. 2.2 Various interaction energies on the kT scale.

The kT criterion can be generalized to gauge the interaction strength between molecules; as stated above, if the
interaction between molecules in a medium is larger than 9.5 kT at a given temperature, then this interaction will
dominate over the thermal fluctuations and form a condensed phase, due to aggregation, adsorption, or self-assembly.
For interaction energies, the use of the kT energy scale is convenient, as 1 kT equals the thermally induced 3D Brownian
motion energy of a molecule (surfactant, or solute, or particle), which provides a reference value of interaction energies
for molecules sticking together vs fly apart, binding vs unbinding, etc. (Fig. 2.2). Fig. 2.2 provides a variety of inter-
action energies represented on the kT energy scale.
Similarly, the kT factor is also met in kinetics. For example, the Arrhenius equation per molecule is
Ea
k ¼ Ae kT (2.8)
where Ea is the activation energy barrier and k is the rate constant of the reaction. If, for example, Ea is much larger
than kT, then the reaction rate is also very small. On the other hand, if the energy barrier is comparable to kT, then the
reaction rate is high, and the reaction can be activated by the thermal energy.
The kT factor is also encountered in the Boltzmann distribution, which is a probability distribution that gives the
probability of a state to exist function of the state’s energy and temperature and it is given by


Ei
exp 
kT
P¼ n
 (2.9)
X Ej
exp 
j
kT

where P is the probability of state i, of the energy Ei, and n is the total number of accessible states of corresponding
energies Ej (j¼1 n). The Boltzmann distribution describes the distribution of particles, such as atoms or molecules, over
all accessible energy states. In a system consisting of many particles, the probability of picking a random particle with
the energy Ei is equal to the number of particles in state i divided by the total number of particles in the system, that is,
the fraction of particles occupying the state i:


Ei
exp 
Ni kT
Pi ¼ ¼ n
 (2.10)
Ntotal X Ej
exp 
j
kT
8 2. Thermal energy scale kT

The denominator in the above equation is the partition function 1/Z:

1 1
¼ n
 (2.11)
Z X Ej
exp 
j
kT

Reference
[1] J. Israelachvili, Intermolecular and Surface Forces, third ed., Academic Press, San Diego, CA, 2011.
 C H A P T E R

3
Surfaces and interfaces

An interface is the boundary between two immiscible phases in contact, such as liquid-liquid, liquid-solid, liquid-
air, etc. Immiscibility arises when the constituent molecules interact stronger with the molecules from the same phase
than with the molecules from the other phase, i.e., the “cohesion forces” are stronger than the “adhesion forces.” The
force of cohesion is defined as the sum of the forces that act between the molecules of the superficial layer and the bulk,
while the forces of adhesion are defined as the forces that act between the superficial layer and the molecules of the next
phase.
The interface is characterized by a certain thickness, which is intuitively taken as the thickness of the last layer of
molecules at the surface of the phase that enter in “contact” or “feel” the influence of the molecules in the other phase. It
has been the subject of intense research where exactly lies the borderlines defining the interface between two phases in
contact. This can be simplistically defined as two monolayers thick, one monolayer at the interface belonging to one
phase and the other monolayer to the next phase (Fig. 3.1). This is probably the most satisfactory way to intuitively
understand the interface thickness. However, this not very rigorous, because the molecules from subsequent layers
also feel the presence of molecules from the other phase via “longer ranged” forces that operate and whose intensity
decays with the distance from the interface. Michael C. Petty stated that “if the molecules are electrically neutral, then
the forces between them will be short-range and the surfaces layer will be no more than one or two molecular diam-
eters; in contrast, the Coulombic forces associated with the charged species can extend the transition region over con-
siderable distances” [1].
The experimental studies of the neat liquid-liquid interfacial thickness revealed that the hexadecane-water thickness
is about
6 Å by X-ray reflectivity and
15 Å by neutron reflectivity [2]. The apparent discrepancy comes from the
limitation of the both methods which include two contributions, namely the intrinsic width of the interface “that char-
acterizes the crossover from one bulk composition to the other and a statistical width due to thermally induced cap-
illary wave fluctuations (ripples) of the interface” [2]. This also reflects the difficulty of the experimental methods to
probe the interfaces at molecular length scales. The X-ray reflectivity studies of the thickness of the mercury-water
interface was
5 Å, which is comparable to that of mercury-vapor interface of
5 Å and that of pure water-vapor inter-
face
3 Å [3]. These and other studies have revealed that the liquid-liquid and liquid-vapor interfaces are at least two
monolayers of molecules or atoms.
Recently, combined surface vibrational spectroscopy and molecular dynamics revealed an even more complex
aspect of interfaces; in addition to interfacial thickness variation, molecular structuring by ordering and layering of
molecules near interface were observed [4]. The characteristic molecular vibrations were probed at the water-
chloroform and water-dichloromethane interfaces as a function of interfacial depth. From the concentration profiles
of both water and organic solvent molecules it was observed that both the dichloromethane and water extended dee-
per into the opposite phase forming a thicker interface, while the water-chloroform interface was sharper. Near the
water-chloroform interface water monomers were detected, not associated via H-bonds and the concentration profile
of chloroform deeper into the bulk organic phase is oscillatory suggesting the CCl4 molecules are layered near the
interface, not observed for dichloromethane. Numerous examples of ordering and structuring of molecules near
the interface were reported, as well as the consequences, for example, surface freezing of the top molecular layer
of alkane at alkane-vapor interface is 2–3°C higher than the freezing temperature, while this was not observed at
an alkane-water interface, which suggests an increased ordering of alkane molecules in the former case [2].

Chemistry of Functional Materials Surfaces and Interfaces 9 Copyright © 2021 Elsevier Inc. All rights reserved.
https://doi.org/10.1016/B978-0-12-821059-8.00009-0
10 3. Surfaces and interfaces

Molecular modeling also helped in gaining insight into the interfacial boundaries. It was found that the water-
hexane interface is very sharp and is about two monolayers thick [5]; the water molecules near the hydrophobic inter-
face are oriented such that the molecular plane and the dipole moment are parallel to the plane of the interface and the
long axis of the hexane molecules is also parallel to the interface [5, 6]. In addition, some of the water molecules at the
hydrophobic interfaces are incapable of hydrogen bonding, about one in four molecules exhibit dangling hydrogen
bonds, which gives rise to a large interfacial energy [7]. On the other hand, water molecules near strongly polar inter-
faces such as quartz are capable of hydrogen bonding and are oriented in an ice-like structure and no dangling bonds
were observed in surface vibrational studies with vibrational sum-frequency spectroscopy [7].
The consequence of the molecular orientational ordering, layering, reduced capability of molecular bonding, and
interfacial mixing lead to a change in the solvent properties near the interface. For example, second-harmonic gener-
ation in combination with solvatochromic surfactants of different lengths known as “molecular rulers” were able to
probe solvent polarity with depth near the weakly and strongly associating water-organic solvent interfaces. For exam-
ple, the solvent polarity near the weakly associating water-cyclohexane interface quickly converges from the aqueous
to the organic limit in less than 9 Å, while the strongly associating water-1-octanol interface revealed a transition region
of ordered octanol molecules at the interface giving rise to a hydrophobic barrier [8]. The chemical structure and the
molecular dimensions greatly affect the thickness of the interface. Further systematic studies performed with
“molecular rulers” revealed that at the water-organic solvent interfaces the interface thickness and polarity strongly
depend on the molecular structure [9, 10].
The conclusion that can be drawn from experimental evidence is that the interface can be visualized as a sheet or as a
thin “membrane” with certain thickness. The thickness of the interface depends on the ability of the phases to interact
given by the balance between the adhesion and cohesion forces. For weakly interacting phases the interface thickness is
nearly two monolayers thick (Fig. 3.1A), while for strongly interacting phases the interface will be thicker than two
molecular monolayers (Fig. 3.1B). In addition, the polarity gradient across the interface can change due to molecular
ordering at the interface, which propagates to a certain depth in bulk, depicted as a color gradient in Fig. 3.1B.
The membrane separating two immiscible phases has therefore boundaries and is an open thermodynamic system
because it can exchange matter and energy with the neighboring phases. Molecules move continuously to and from
interface to bulk. A thermodynamic system is everything that has boundaries, an object constitutes a thermodynamic
system, be that a car, a grain of salt, or an interface, and all possess a certain internal energy, U. The energy of the
interface between the phases, also most commonly referred to as “interfacial energy,” is highest when the cohesion
energy is much larger than the adhesion energy. Interfacial energy decreases to negligible values when the adhesion
forces become comparable to cohesion forces and the phases begin to mix. Water-hexane interface is an example of a
high interfacial energy interface while water-ethanol interface has a zero interfacial energy, i.e., completely miscible.

FIG. 3.1 (A) The ideal sharp inter-

face between two weakly interacting
phases α and β can be imagined as a
thin membrane, two monolayers
thick with a sharp molecular density
profile that separates two phases.
(B) The thicker interface between
two phases that are strongly interact-
ing with diffuse density profile,
thicker than two monolayers. The
oscillation in the β phase indicate
ordering. The solvent polarity near
this interface changes due to order-
ing and loss or gain in bonding
capability.
 3.1 Surface tension of liquids 11
The molecules at the interface have energy higher than those in the bulk because they are not symmetrically sur-
rounded by other “alike” molecules in a perfectly balanced sphere. This imbalance of attraction forces and suppression
in the ability of the molecules to bond lead to more energetic molecules at the interface.

3.1 Surface tension of liquids

In the bulk, a molecule or an atom can be surrounded by a maximum 12 neighboring molecules (6 in the same plane
and 3 on each side of the neighboring planes) and experience a symmetric attraction from all sides in the 3D space. On
the other hand, at the surface of a liquid the molecules are about only half-way surrounded by molecules, thus expe-
rience an asymmetric attraction toward the bulk of the liquid (see Fig. 3.2A). The forces of cohesion act asymmetrically
on the interfacial layer and the topmost layers of molecules of a phase are compressed (Fig. 3.2B).
In addition to the cohesion forces that act perpendicularly on the surface plane, the surface tension forces act in the
plane of the surface and oppose any action to increase the surface area. Surface tension can be intuitively understood as
a unit vector force. To visualize this, an imaginary line can be drawn, of length l, on the surface of the liquid; this imag-
inary line splits the row of two molecules (Fig. 3.3) If it were possible, by pulling apart the two rows of molecules on the
surface of the liquid, a resisting tension force would arise because the molecules from each row attract each other gen-
erating a tension opposing the split (Fig. 3.3A).
If the length of this dividing line is l, then the force with which the pair of molecules in the two rows attracts each
other is.
F¼γl (3.1)
where γ is the unit tension force (N/m), i.e., the surface tension. Therefore, the surface tension γ is the unit force acting
on the surface plane to minimize the surface area.
To better understand the origin of the surface tension, we imagine a cross section through the surface of a liquid
(Fig. 3.3). At equilibrium no net force is acting on this horizontal line (plane) of molecules. If it were possible, the pull of
only one molecule out of this line (plane) would be countered by an opposing tension force trying to minimize the area
of the surface layer. The unit surface tension forces act left and right on the molecule being pulled out of the line and the
sum of these is the cohesion unit force (Fig. 3.3C). It costs energy to bring new molecules from the bulk to surface. When
surface is expanded, more “bonds” from the bulk are “broken” as new molecules are brought to occupy the “holes” in
the newly created surface, represented by the dotted circles in Fig. 3.3B. The energy of the molecules in bulk of the
liquid with maximum of 12 neighbors is lower than the energy of the molecules at the surface with the maximum
6 neighbors. The energy required to bring a molecule from the bulk to increase the area of the surface is the energy
of uncompensated bonds; at the surface, a molecule has about half of the neighbors of a molecule in the bulk, half of its
“physical bonds” remain uncompensated (Fig. 3.3B). Therefore, the surface energy is only a fraction of the cohesion
energy as explained later in more detail.

FIG. 3.2 (A) Molecular interactions in a liquid; (B) compression of the topmost surface layer of molecules due to the force of cohesion.
12 3. Surfaces and interfaces

FIG. 3.3 (A) Surface of a liquid on

which an imaginary line of length l
divides two parallel rows of mole-
cules; when trying to pull sideways
the two rows of molecules by apply-
ing a force F on each side, the surface
tension forces oppose the distancing
of molecules; the surface tension unit
vectors are oriented perpendicular to
the imaginary line. (B) Deformation
of the liquid-gas interface by pulling
only one molecule out of the surface;
in this case two new empty “holes”
(dotted circles) are created by the
expansion of the liquid-gas interface.
Two new molecules must be brought
in from the bulk liquid to occupy the
empty holes, depicted by the green
curved arrows. The total energy of
the interface will increase by an
amount equal to the energy of
uncompensated bonds of the new
molecules occupying the holes.
(C) Same situation as in (B) with the
depiction of the opposing surface ten-
sion forces resisting the deformation.
The vectorial sum of the surface ten-
sion vectors acting on the molecule
being pulled out of the interface is
the cohesion force acting on the
molecule.

FIG. 3.4 Forces acting on a steel needle, with a hydrophobic surface, floating on the surface of water without penetration.

Numerical example 3.1

Draw the surface tension force vectors acting on a steel needle with a hydrophobic surface floating on the surface of water
depicted in Fig. 3.4. The needle does not penetrate the surface. Calculate the maximum radius of a steel needle r, of length
l ¼ 1 cm that can be held on the surface of the water without sinking. The density of steel is 8000 kg/m3, ρwater ¼ 1 kg/dm3,
γ water ¼ 73 mN/m.
 3.1 Surface tension of liquids 13
Solution
When the steel needle does not penetrate the surface, it means that the water does not wet the surface of the needle, in which
case the water contact angle with the surface of the needle is θ ¼ 180 degrees. In addition, the water surface will suffer a certain
deformation such that the resultant of the forces acting at the three-phase line will be oriented vertically, against the pulling
gravitational force acting on the needle.
At equilibrium the surface tension force balances the gravitational force:

2Lγ L ¼ mg
Therefore, R can be directly calculated:

1=2
1=2
2γ L 2  0:0728
R¼ ;R¼ ¼ 0:77 mm:
πρg π  8000  9:81

Numerical example 3.2

A wooden stick of the length l floats on the surface of pure water. If we lower the surface tension of water by adding a droplet
of soap on the right side of the stick, in which direction will the wooden stick move? Under the action of which force? Write
down the equation for this force.

TABLE 3.1 Surface tension of several liquids and molten metals to compare the surface tension to the strength of
intermolecular interactions.
Liquid Surface tension (mN/m) Temperature (°C)

Neon 5.2 247

Oxygen 15.7 193
Ethyl alcohol 22.3 20

Olive oil 32.0 20

Water 58.9 100
66.2 60
72.8 20
75.6 0
Mercury 465 20

Silver 800 970

Gold 1000 1070
Copper 1100 1130
14 3. Surfaces and interfaces

The surface tension of various liquids changes with temperature. The magnitude of the surface tension reflects the
strength of interaction forces between the composing molecules and atoms, i.e., the cohesion forces (Table 3.1). For
neon the strength of the interaction forces between atoms are very weak and the surface tension reaches 5.2 mN/m
at 247°C. The cohesion forces are comparatively stronger for oxygen molecules than for neon atoms. Metallic bonds
between mercury atoms are considerably stronger than the van der Waals forces between neon atoms, therefore even
at room temperature the surface tension value is comparatively large.

3.2 Predictive models for calculating the surface tension of liquids

There were attempts to apply theoretical models to calculate the surface tension from the energy of cohesion or
enthalpy of vaporization. For example, Stefan’s equation has been often used to do this [11]:
2 3
ZS 4ΔHvap ρ =3 5
2

γL ¼ (3.2)
Z 1
=
M =3 N A 3
2

where Δ Hvap is the enthalpy of vaporization of the liquid (kJ/mol) in standard conditions of pressure and temperature
of 105 Pa and 273.15 K, respectively, M is the molecular weight (g/mol), NA is the Avogadro number, and ρ is the
density of the liquid (g/cm3). ZZS is the ratio between the coordination number of molecules at the surface with respect
to bulk; this cannot be determined directly by experiment but can be calculated [12]. The ratio of the coordination num-
bers for the compounds ranges from 0.0559 to 0.1784, whereas a value 0.25 for the ratio ZZS has been obtained for many
organic substances [12].

Numerical example 3.3

Calculate the surface tension of water using Eq. (3.2) knowing that ΔHvap ¼ 41 kJ/mol, M ¼ 18 g/mol, ρ ¼ 1g/cm3, and ZZS ¼
0:13 is the average value of all the determined values by Strechan et al. [12].

Solution
 

1=3 !
41  104 KJ mol 2=3  g 2=3 mol mJ
γ water ¼ 0:13    ¼ 76 2 (3.3)
6:86  8:44  107 mol g m3 molecules m

The obtained value slightly overestimates the experimentally determined value of water surface tension 72.4 mJ/m2 at room temperature.
Therefore, the correct calculation of ZZS is important for obtaining accurate values of the surface tension.

Significant effort has been dedicated to modeling the coordination number ratio ZZS .
Another extendedly used empirical model, especially for determining the surface tension of molten metals, is called
the bond-broken model or the bond-cutting model where the surface energy is calculated based on the energy of cohe-
sion Ecohesion [13]:
Z  ZS
γL ¼ Ecohesion (3.4)
Z

3.3 Interfacial tension between liquids

Surface tension is only a particularization of interfacial tension and it is used only when referring to liquid-gas (vapor)
interface. Interfacial tension refers to liquid-liquid or solid-liquid interfaces, but because it is a more general concept
than the surface tension it can be used throughout, also for liquid-gas interfaces. For liquid-liquid interfaces, the top-
most layers of molecules from each phase are in contact (Fig. 3.5). In contrast to the liquid-gas case, the topmost layer at
the liquid-liquid interface will now be under the action of two forces, forces of cohesion with the molecules from the
bulk of the same phase and forces of adhesion with the molecules from the other phase. Consequently, the topmost
layer of liquid is not as strongly compressed as at the liquid-gas interface. The stronger the forces of adhesion, the
stronger the attraction of the topmost layer to the second liquid phase.
 3.3 Interfacial tension between liquids 15

FIG. 3.5 Balance of the forces of cohesion with the force of adhesion at the liquid-liquid interfaces.

FIG. 3.6 (A) The surface tension vectors corre-

sponding to liquid 1 and liquid 2 oppose the defor-
mation of the liquid 1-liquid 2 interface. Interfacial
tension vector is depicted here as the sum of the sur-
face tension vectors of the pure liquids, but does not
sufficiently describe the real situation. (B) The force
needed to deform or expand the interface is lower
because the opposing force due to the surface tension
is now minimized by the adhesion forces with the
molecules in the second phase. In other words, to
promote a molecule from bulk to interface it costs
much less energy at the liquid-liquid interface
because the intermolecular bonds in bulk are now
partially compensated at the liquid-liquid interface
by the adhesion bonds with the molecules from the
surface of the second phase. (C) The balance of forces
at equilibrium, the surface tension force is compen-
sated by the adhesion force.

Opposing deformation of the interface between two liquids, as depicted in Fig. 3.6A, is the interfacial tension unit
vector γ 12. It can be imagined that γ 12 is exactly the sum of the surface tensions of the two liquids, γ 1 and γ2. In fact, the
force of adhesion between the two liquids makes γ12 smaller than the sum of the surface tension corresponding to each
liquid. It costs less energy to bring a molecule from the bulk to the liquid-liquid interface than to the liquid-gas inter-
face. This is because breaking of the “bonds” of cohesion of the bulk molecules to come at the interface will be partially
compensated by the adhesion “bonds.” Therefore, γ12 is the sum of two surface tension minus twice the force of adhe-
sion (Fig. 3.6B and C):
γ 12 ¼ γ 1 + γ 2  2Fa (3.5)
16 3. Surfaces and interfaces

FIG. 3.7 (A) U-shaped wire

frame holding a thin liquid film
membrane which has a mobile side
of length l that can slide under the
action of an external force; (B) the
cross section of the liquid mem-
brane film having two surface ten-
sion forces, corresponding to each
interface of the liquid membrane,
opposing the expansion of the sur-
face area under the action of the
pulling force F.

Two extreme situations can be distinguished, if Fa is very high and comparable to the cohesion forces, then γ 12 ! 0 and
the two liquids can easily mix and will not form an interface. If, however, the molecules between the two phases are
incapable of “bonding” or Fa is extremely low, then γ12 ! γ 1 + γ 2, consequently it is more difficult to expand or deform
this interface.

3.4 Relating surface tension to surface energy

The surface tension is a force per unit length. However, the surface tension can also be related to energy per surface
area, or energy density. Consider a wire frame with one mobile side, which can slide on the U-shaped frame without
friction (Fig. 3.7). The mobile side has a length l. On this frame we have a membrane of water, a thin film. If we try to
pull the mobile side to increase the area of the membrane by Δx, then the work done will be
W ¼ F  Δx (3.6)
but F is 2γl, the factor 2 comes from the fact that there are two sides of the surface. Therefore, surface tension is also the
energy per unit area:
W Energy 
γ¼ ≡ J=m2 (3.7)
2l  Δx Area
The surface tension can thus be redefined as the energy required to increase the surface area with one unit.

3.5 Surface and interfacial energy of solids

Surface and interfacial tensions have units of force per unit length N/m or energy per unit area J/m2 and the two
forms are perfectly equivalent. For the solid-gas interfaces instead of interfacial tension one uses the concept of “surface
energy.” Similarly, for the solid-liquid interfaces “interfacial energy” is used instead of “interfacial tension.” The sur-
face energy of solids arises because of all unsaturated or dangling bonds per unit area of surface of a solid. Surfaces of
metals, for example, have high energy associated with them because the atoms in the first surface layer have fewer of
neighbors than in bulk and therefore unsatisfied capacity to metallic bonding. The cohesive energy of metals is given
by the enthalpy of atomization ΔHa (equivalent to its bond strength), which is 418 kJ/mol for Fe, 844 kJ/mol for W,
368 kJ/mol for Au, and 327 kJ/mol for Al [14]. A great amount of work is needed to form and shape metals of high
cohesive energy. The surface energy is taken as a fraction of the cohesion energy, γ ¼ f  cohesion energy, 0 < f < 1. In
calculations of the surface energy from energy of cohesion, f could arbitrarily be chosen as 0.5 (see Fig. 3.3). There are
roughly 1.6  1019 atoms/m2 on the surface of an Fe and the surface energy can be estimated from the cohesion energy:


kJ atoms mJ
SE  0:5  418  1:6  1019  5535 2 (3.8)
6  1023 atoms m2 m
The surface density of metal atoms Nd was calculated from the density of the metal: Fe (ρ ¼ 7850 kg/m3, Nd ¼ 1.6  1019),
W (ρ ¼ 19,600 kg/m3, Nd ¼ 1.32  1019), Au (ρ ¼ 19,320 kg/m3, Nd ¼ 1.25  1019), and Al (ρ ¼ 2712 kg/m3,
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"He doesn't know what a privilege he has just had," she said laughing. Then
she looked down at the child, "I do hope he will be a good man like his father,"
she murmured.

"So thank God, she still loves her absentminded husband as much as ever!"
thought the Bishop, but he felt he could have shaken him. To possess such a
treasure and not take more care of her was in his opinion reprehensible in the
extreme. They were a blind pair! He to her lovely self-forgetfulness, and she to
his absentmindedness. Well, he was thankful that she was still devoted to him.

Rachel laughed when she discovered that the Bishop had made her bovril
himself! It was luxury to be looked after and taken care of.

Before he left, he made her promise to have medical advice.

"It would never do for me to see a doctor," she expostulated, "and I have no
time in which to be ill. What do you suppose Luke would do with an invalid
wife, and little Pat with a useless mother! No, it won't do to give in and it was
only the sudden sight of you that made me so stupid."

"It is only right to both your husband and child that you should consult a
doctor," returned the Bishop. "Possibly all you need is a tonic; anyhow, as I
consider I stand in the position of a father to you, you must do what I say. And
you must certainly curtail your work."

And so Rachel gave way and promised, and the Bishop left the house with a
heavy heart. Besides the state of Rachel's health he had learnt for the first
time of their extreme poverty of which he had had no idea. He did not suppose
that Rachel's family knew the state of their finances, as Gwen would certainly
have enlarged upon it in her letter to him had she known. No doubt Rachel
had hidden the fact from her mother partly to save her pain, and also to
prevent her from blaming Luke for marrying her when he could not provide for
her. Something must be done. He was unwilling to give Luke too sudden a
shock by telling him what he thought of his wife's health, but as Mrs. Greville
was now getting stronger, he decided to enlighten her quickly about the
matter. He would write directly he got home; and meanwhile, the thought that
this was only one case of extreme poverty that existed among the clergy in his
diocese, lay on his heart like lead.

But the doctor told Mrs. Greville of the serious state of Rachel's health before
the Bishop's letter reached her.
 CHAPTER XXII.
THE DREAM OF HIS LIFE.

Rachel did not hurry to see a doctor, but having promised to do so she knew
she must keep her word, so the second day after the Bishop's visit, knowing
that Luke would be away at a clerical meeting in the country, she wrote a note
to the doctor who had been attending her mother-in-law asking him to come
and see her. She did not suppose that there was anything seriously the matter
with her notwithstanding the fact that she felt so ill; and after all, she thought
to herself, she need not follow out his injunctions if they were inconvenient.

She was quite unprepared for his verdict. He told her that both her heart and
her lungs were affected, and that it was absolutely necessary that she should
give up all parish work and if possible take a thorough rest. To Mrs. Greville,
he gave a still more serious account.

"She should leave this place at once," he said, "and live as far as possible an
open air life. A sanatorium would give her the best chance. But if this is
impossible she should go into the country or to the sea. Of course she has
been doing the work of two or three women. She must drop all that and what
is more she should be fed up. She is not properly nourished."

"Do you mean to say you think that she has not had enough food?" asked
Mrs. Greville very much distressed.

"I am afraid not. She has not looked after herself at all. I made her tell me
what she had had in the way of food yesterday, and when I heard I was not
surprised at her state of health.

"I am afraid it will be an awful blow to my son," said Mrs. Greville.

"I'm afraid it will, but if he wants to keep her he must make some other
arrangement for her. I won't be responsible for her life unless she is removed
as soon as possible, and is given the opportunity of changing entirely her way
of living."

Mrs. Greville so dreaded telling Luke the news she had received from the
doctor that she did not ask him to come round to see her that evening. So she
sat and brooded over the news, and in her heart she blamed Rachel for
neglecting herself as she had evidently done. Of course people would lay the
blame on Luke; but how could you expect a man whose every moment was
filled in with his parish duties to notice when his wife looked pale, or lost her
appetite. And what a terrible hindrance to his work to have an invalid wife!
Moreover, it was easy for the doctor to prescribe a different climate and
complete rest; but how his plans were to be carried out she did not know.

Meanwhile Rachel quite unconscious of the doctor's visit to Mrs. Greville, after
the first shock of the news, determined to behave as if he had never been.
She was resolved not to become an invalid and a hindrance to her husband,
an hour before it was positively necessary. And after all doctors often made
mistakes. She would drink more milk, a matter on which he had laid great
stress, and there she would leave it.

When Luke returned home from the clerical meeting he was in good spirits.
The paper he had read had been well received and the discussion that had
followed had been intensely interesting. Rachel was as interested in all that
had happened as she always was in his concerns, and he did not notice that
she was looking unusually tired and worn.

The next day two letters lay on the hall table for Luke. But he had to hurry off
directly after lunch to an appointment, and so he put them in his pocket to
read in the tram on the way.

It was only after taking his seat that he remembered them. One he saw at
once was from the Bishop, the other had the London postmark. He opened
the second first as being more interesting to him; and he could scarcely
believe what he read. It was the offer of a living in a crowded part of London,
where he would have the charge of 16,000 souls. He could have shouted for
joy. It was exactly what he had been longing for. It was true that financially it
was not much better than his present living, but money had very little
attraction or indeed meaning for Luke, and he dismissed from his mind that
part of the news in the letter almost without a thought. It was the work that he
craved, and work in the very centre of the universe, as he liked to think of
London. At last the dream of his life was coming true. He felt he could hardly
get through his work, so anxious was he to tell the news to Rachel and to his
mother.

He felt that his mother would rejoice with him almost more than Rachel. Now
that he came to think of it his wife had never taken much to the thought of
London; though he knew that she would do nothing to prevent him going. Had
she not said when they had been talking about the possibility of him one day
being offered a church there, "Where thou goest I will go?" But the
remembrance of her words about London and her dislike of it, for a moment or
two rather damped his spirits; but he knew she would not fail him now that the
dream of his life was coming true.

So full was he of the news the letter contained, that he forgot there was
another one in his pocket till he was in the tram again on his way home.

To his amusement, he found that this one was also an offer of a living; but one
in the country. It was a good one, much better than the one offered to him in
London; but this did not weigh with him in the least, and the fact of it being in
the country at once made him dismiss it from his mind. In fact, he scarcely
took in the Bishop's letter in which he said, that he felt sure a country life
would be beneficial both for his wife and his son, adding that when he called
at his house he had thought Rachel looking very tired and worn.

Rachel was always so bright in her husband's presence that he supposed the
Bishop must have called at an inconvenient time and that unfortunately
Rachel had not been able to conceal the fact. He had not noticed anything
wrong in her looks himself, and he did not recollect her once complaining of
even a headache ever since her marriage. The Bishop evidently had got a
wrong impression of her from his call. He would write and thank him for his
kind thought of them but decline the country living and tell him why. Then he
thrust the Bishop's letter into his pocket and made his way joyfully toward his
mother's rooms.
 CHAPTER XXIII.
LUKE SEES HIMSELF.

Luke, full of his great news, ran upstairs to his mother's room, with the letter
from London in his hands.

He found her crouching over the fire in the big horsehair chair, the only
armchair in the room. He was surprised that she did not look round at the
sound of his footsteps and give him her usual smile of welcome. Instead, she
stretched out her hand to him with averted eyes.

"Mother what is it?" he asked. He knew she must have bad news of some kind
and wanted to express her sympathy before she broke it to him.

"My poor boy," was all she said.

Luke took a chair by her and looked anxiously at her. She had been so much
better lately, was able to walk a little and was getting altogether stronger, that
her action perplexed him. Had the doctor given her a depressing account of
herself, he wondered? Mrs. Greville's first words confirmed this fear.

"Dr. Fleming has been here."

"And surely he thinks you much better? Don't let him make you nervous about
yourself, mother."

"It isn't about myself," said Mrs. Greville in a strained tone of voice, "it's about
Rachel."

Luke's face cleared at once.

"Oh well," he said laughing, "you may make your mind easy about her. I left
her this morning in good spirits."

He was much relieved.

"My poor boy!" said his mother again, "You must prepare for a great blow."
He began to wonder if the slight stroke his mother had had, affected her brain.
He put his hand caressingly on hers. "Let's have it out," he said with a smile. "I
don't think what ever it is that it can affect me as much as you imagine."

"Rachel is not well," said his mother watching his face anxiously. "She saw the
doctor yesterday."

"Not well!" said Luke astonished. "Why, what is the matter with her? She was
quite well anyhow this morning. Has she had an accident?"

"No. It is worse than an accident. The doctor thinks very seriously of her."

Luke rose and stood before his mother. All the colour had left his face.

"Tell me outright what you mean," he said sharply. "What is wrong with her?"

"Both her heart and her lungs."

Luke stood quite still and silent. He was always silent and unnaturally quiet
when agitated in his mind.

"When did she see the doctor?" he asked at last.

"Yesterday."

"Yesterday!"

"Yes. The Bishop, you remember, called on her. He made her promise to
consult him."

"And why didn't she tell me?" said Luke. And the agonised expression in his
eyes showed his mother how intensely he was moved.

"I don't know, except that she wanted to save you anxiety. She has not told me
either and I don't suppose that she has any idea that Dr. Fleming came round
to see me about her."

Luke dropped into a chair. Then he looked up again at his mother.

"Did he give any directions or say what should be done?" he asked.

"I'm afraid he did my dear boy. He mentioned something about a Sanatorium,

but anyhow, he said it was absolutely necessary for her to have perfect rest
and a change of air and environment. In fact Luke," she added, and her voice
trembled, "he seemed to think it a matter of life and death."

Luke groaned and covered his face with his hands.

"He says," continued his mother, "that she has evidently been doing too much
and has not taken care of herself. He particularly dwelt on her thinness.
Apparently she has not had nourishing food."

Luke groaned again.

"I feel Rachel is greatly to be blamed for having been so careless about her
health," added Mrs. Greville.

Luke looked up, and his mother was startled by the stern expression of his
face.

"Rachel to be blamed!" he repeated. "I am to be blamed, not Rachel."

There was anguish in his tone of voice. He picked up the letter from London
which had fallen to the ground, ramming it into his coat pocket. Then he
sprang up and looked at his watch.

"I shall go and see the doctor at once," he said. And without another word, he
hurried away.

His visit confirmed his worst fears, and the doctor seemed surprised that he
had never noticed the gradual change in his wife's appearance. Even he had
seen it, casually meeting her in the street.

Luke walked home as if in a dream. The letters in his pocket were absolutely
forgotten; his one thought was Rachel.

He opened the door of the house softly and went up into his study. He felt he
could not meet his wife till he had looked the terrible truth in the face. The
thought that he might possibly lose her was too painful to him to be able to
bear calmly, and yet he knew that he must not give her any hint as to his
fears.

He shut the door of his study after him and sank into the large armchair by the
fire burying his face in his hands.

The fire! Even that seemed to cry out in condemnation of his selfishness. Of
course Rachel had lit his fire so that his room might be warm and comfortable
for him, while she probably had had no fire to sit by except that in the kitchen.
He had been so preoccupied with his own interests and concerns that he had
scarcely given a thought to hers. His mother had said, that the doctor gave it
out as his opinion that she had not eaten enough. How was it that this fact had
never been noticed by him! She always supplied him with plenty, and it had
not struck him to notice what food she had provided for herself. Husband and
child had never wanted for anything.

The doctor had said that she was thoroughly overworked. And yet he had
never noticed how she was getting thin and pale! How often had he asked her
to do things for him so that he might go off to some meeting or other, and it
had never crossed his mind that the anxiety of leaving Pat with inexperienced
Polly must have added to the strain.

Then he had never shared in the care of the child; in fact he had at times
asked Rachel to do what she could to keep him quiet as his crying somewhat
disturbed him working. Not many weeks after his birth he had moved his bed
into his dressing room, as the child's restlessness prevented him sleeping,
and he felt his sleep to be all important to his work. He had never realised that
Rachel also wanted an occasional night's rest.

And what had she not given up for him! Her luxurious home, where she had
every comfort; her mother and sisters who had petted and loved her; her out
of door pursuits; her flowers which she loved so passionately; her ease and
her friends. And what had he given up for her in return? Nothing! Nothing!

In exchange for all her home comforts, he had given her a pokey little house,
poverty, overwork, and strain!

He was indeed in the Valley of Humiliation!

Then he suddenly rebelled at his thoughts and he started up and began to

pace the room. Given her nothing! He had given her his heart's love. All the
love that he knew how to give. Next to his God was his love for his wife; and
he knew that in this sudden reaction of thought Rachel would be one with him.
Though poor compared to her love for him he had given her his best. She
knew she was all the world to him. Life without her was unthinkable. He
paused as he reached his writing table, looking down absently at his Sunday
sermon which he had already begun. The text of it faced him.

"'These ought ye to have done, and not to leave the other undone.'"
The words gave him a shock. They so exactly described him, and yet he had
been so unconscious of his delinquencies that he had actually intended to
preach to his people about theirs.

"'These ought ye to have done, and not to leave the other undone.'" The Word
of God condemned him. He had forgotten that preaching and visiting were not
the only duties to be done for God, or the only work. Did not St. Paul lay a
special stress on the home life?

He realised now that though he loved his wife so devotedly, he had been so
engrossed in his own affairs that he had neglected her. He suddenly paused in
his walk. That was Rachel's voice. Evidently little Pat was restless and his
mother was singing him to sleep. Luke could hardly bear the sound of her
dear voice. It pierced his heart like an arrow. He pictured just how she was
looking, walking up and down in her bedroom with the child in her arms. He
had often heard her sing the words that he now heard, but he remembered
how even the sound of her singing at times had disturbed him, and he had
asked her to stop. But this evening, he listened and wept.

"Away in a manger, no crib for a bed,

The little Lord Jesus laid down His sweet head,
The stars in the bright sky looked down where He lay,
The little Lord Jesus asleep in the hay."

"The cattle are lowing, the baby awakes,

But little Lord Jesus no crying He makes.
I love Thee Lord Jesus! look down from the sky,
And stay by my side until morning is nigh."

"Be near me Lord Jesus; I ask Thee to stay

Close by me for ever, and love me I pray.
Bless all the dear children in Thy tender care,
And fit us for Heaven to live with Thee there."

The voice grew softer and softer; then it ceased altogether and Luke knew Pat
was asleep.

He so dreaded to meet Rachel that he stayed up in his study till he heard her
footstep outside. When she opened the door she found him sitting over the
fire in an attitude of deep depression, and knew at once that somehow he had
learnt the news about her. Kneeling by his side she laid her head on his
breast.

"You mustn't worry about me dearest," she said, "I think myself that Dr.
Fleming is a pessimist and has made a mistake. Anyhow I don't mean to act
as if what he said was true. I shall just go on as I have done before; that is to
say after a little rest. I suppose I must have that."

Luke was silent. He hardly thought that she could be aware of her serious
condition.

"Why did you not tell me?" he asked after a pause. There was a tone of
reproach in his voice.

"I didn't want to worry you, you have so much to trouble you. Besides, I don't
suppose there is anything really the matter with me. Doctors make such
mistakes."

He took up one of her hands and looked at it. He was shocked to notice how
thin it was.

He held it to his lips and kissed it. The unusual action almost broke Rachel's
self-control.

She rose saying, "I must go now and see after the supper. Polly will wonder
where I am." But once out of the room her tears began to flow.

"Oh, I mustn't be ill," she gasped, as instead of going into the kitchen, she
sank into a chair in the drawing-room. "I shall be no good to Luke, only an
anxiety. Oh God show me what to do. Don't let me be a burden to him."

Luke, after Rachel had left, sat sunk again in deep depression.

Then suddenly he remembered the letters in his pocket. He had completely

forgotten them, and now when he opened for the second time the Bishop's
letter, it suddenly dawned upon him that here was the way out of his difficulty.
To accept the country living meant that Rachel could live in the garden, and
her strenuous life at Trowsby would be over. She would go to the place as a
known invalid and would not be expected to take up parish work. The cloud on
his face lifted, and the weight on his heart grew lighter. Moreover, the struggle
with poverty of which Rachel had been more conscious evidently than he had,
would be over, for the stipend was unusually good.
With a feeling of great thankfulness, he closed the letter and opened the one
from London intending to answer them both that night. Of course the London
living must be refused. There was no question about it. But as he read over
again the description of the work a feeling of intense disappointment took
possession of him. He had been longing for this offer! It was, as he had once
said to Rachel, the dream of his life.

And here it was within his grasp and yet he was unable to accept it. Instead of
preaching to a large congregation and ministering to their souls needs, he
would have to vegetate in the country! It would be a living death to him.

During the first year or two of his present charge he had tasted what it was to
be able to move people by his oratory; it was only the extra-ordinary craze for
amusements that had spoilt it all. It was then he began to long for a wider
sphere, and though the parish in which was the church that had been offered
to him was in a poor part of London, the congregation consisted of many who
had been drawn there by the preaching of the former Vicar. The Trustees
were most anxious to secure a good preacher to succeed him. One of them
had visited St. Marks on purpose to judge of Luke's preaching, and was much
struck by it. This was why the living had been offered to him notwithstanding
the fact that he was somewhat young for such an important post. All this was
mentioned in the letter that Luke held in his hand, and the fact that he had to
decline it filled him with the keenest disappointment. So keen was it that he
decided not to tell Rachel that night about either letter. He would wait to
answer them till the next day. It was never a good thing to do anything in a
hurry.

Luke's silence at supper did not surprise her. She knew that it was a sign that
he had some problem to solve. The problem of course, this evening, she knew
must be what to do about her. Once or twice she tried to make him smile as
she recounted some event of the day; but she was so unsuccessful that she
felt it was better to leave him to his thoughts. She was trying herself to unravel
the difficulty that had arisen, but so impossible did she find it that she came to
the conclusion that the only thing was to leave it in Higher Hands. God had
always provided for them and would do so still. Was He not a very present
help in time of trouble?

Luke sat up late that night. He was standing before the Bar of his own
conscience. He had to face the fact that he was feeling rebellious; struggling
against the Will of God. To bury his talents in a village was a repugnant
thought to him. How could he endure the quiet and dullness of it? Would it not
tend to make him indolent in work? What would be the good of reading all the
new thought of the day in order to help those who were troubled by it, if there
was no-one who had even heard of the false teaching. How could he spend
his time in preparing sermons suitable to men and women whose brains had
never been taught to work. He pictured himself preaching to a congregation,
the half of which were asleep and the other half on the verge of going to
sleep. Then he suddenly remembered how his Lord had spent time over the
soul of one poor woman, the Lord of whom it was said, "Never man spake like
this man." Had He not taught again and again, both by his words and actions,
the value of one individual soul?

Luke's disinclination for a village congregation made him look into his own
motives. Had all his work been at Trowsby been done for the glory of God?
Had not the first year or two of his great popularity somewhat intoxicated him?
Was the wish to preach to large audiences to win them to the service of the
Lord? Or was it the delightful sense of power to sway their minds, that
attracted him? Was the disappointment and the longing for a larger sphere
caused at all by the fact that he was conscious that he had lost hold of his
people? That they no longer hung on his words as of yore; that instead of
looking up to him, as formerly, with admiration, they looked down on him as
out of date?

Sitting by his fire that night, looking at the dying coals, he saw himself for the
first time in the light of one who had been weighed in the balances and found
wanting. He was right down in the Valley of Humiliation, and in agony of soul.

It was late when he went to his room. Then he dreamt that he was a Bishop
preaching in St. Paul's Cathedral. He looked down at the sea of faces, and
was conscious of a thrill of emotion as he saw the vast congregation before
him. He felt triumphant and elated as among the number he noticed some of
his parishioners at Trowsby, who had left his Church because they did not
consider him up to date.

He heard his fine voice echoing down the aisles as he gave out his text, and
was congratulating himself on its texture, when the whole congregation rose
to its feet, saying solemnly and slowly, "Thou art weighed in the balances, and
art found wanting." Then they filed out of the Cathedral till he was left standing
alone in the pulpit, with the condemning words still echoing among the pillars.

He awoke trembling with horror, and knew, in the anguish of his soul, that it
was true of him. He had been weighed in the balances and found wanting.

The cry of his little son in the adjoining room reached him; and he heard
Rachel's soft voice singing:
"Be near me Lord Jesus; I ask Thee to stay
Close by me for ever, and love me I pray.
Bless all the dear children in Thy tender care,
And fit us for Heaven to live with Thee there."

He rose and opened the door softly, and took the child from her arms. Rachel,
almost too tired to smile or feel any surprise, lay down and slept.

"Perhaps," said Luke to himself, "To take care of my little son, may be more to
God's glory than to preach in St. Paul's Cathedral."

He wrote the next morning before breakfast to refuse the London living and to
accept the one in the country; and he never told his wife nor his mother that
he had had a chance of experiencing the dream of his life and had put it away.

CHAPTER XXIV.
FOR LUKE'S SAKE.

Luke paced up and down the lawn of his pretty Rectory. The moon was
shedding its silver light on grass and trees; the flowers were flinging their
perfume around him; a nightingale trilled out its song from a tree in the
distance; but it all meant nothing to Luke. His soul was crying out for crowds of
human beings; for his fellow men; for the rush and excitement of city life; for
the tumult and whirl of London.
The silence of this summer night broken only by the song of the nightingale
was almost unbearable. The thought of his village church sparsely filled with
farmers and their wives, and labourers, who listened to him with their mouths
open in astonishment at the oratory of their new "parson," the remembrance of
the cottages nestling on the hill below the Rectory, with their walls covered
with roses and honey suckle, and whose occupants he had already visited
several times during his short stay among them, had no charm for him.

He longed for strenuous work in courts and alleys, for congregations of people
who could appreciate his sermons; he pined for London platforms and
enthralled listeners to his eloquence. He felt he was wasted, utterly wasted in
this quiet village on the hill that Rachel so loved.

Yes, Rachel loved it. That was the only compensation. Gradually it seemed
that her health was returning. The open air life and comparative rest from
worry were doing their work; and only a few minutes before, she had left him
rejoicing in all the beauty of their surroundings, its peace and quietness. She
revelled in the flowers and trees and soft green grass.

When Luke had told her two months ago of the Bishop's offer of Stagland, the
news had struck her as so wonderful that she had burst into tears. She knew
that a few more months in Trowsby would mean that she would have to say
goodbye to husband and child and leave them to get through life alone; and
the lifting of that burden seemed almost too good to be true. Moreover, living
at Stagland meant an end to the perpetual struggle of keeping within their
means, an end too of housework, for which she was entirely unfit. She
decided before many hours were over to take the faithful little Polly as
nursemaid and to help in the house, with another general servant. They would
be able to grow their own vegetables and fruit, and no doubt Luke would do a
certain amount of work in the garden with a man to help. The whole plan
seemed ideal to Rachel. She lay awake thinking of it at night and panting for
the fresh air of the country.

At times, however, she wondered if she ought to let Luke sacrifice himself to
the extent of living in the country. Would he be able to endure it? Would he
have enough to occupy his time? Was it right that a young and strong man
should take a country living and spend his best years among fields and
hedges instead of courts and alleys?

She looked anxiously at his face when he did not know that her eyes were
upon him, and was afraid that she detected a shade of sadness in its
expression. Luke, however, was very careful not to let her know by his words
how almost unbearable the thought of the country was to him. But when
Rachel was not with him he gave way to his miserable thoughts.

He had been inexpressibly touched by the warmth of feeling displayed by

some of the members of his congregation at Trowsby when they heard that he
was leaving them. As is often the case, he learnt then for the first time that
which would have immensely encouraged him had he known it before, that he
had helped so many of them spiritually. It made leaving them all the harder,
though at the same time it warmed his heart to find that he had been used far
more than he had imagined for the good of their souls. The last two Sundays
at Trowsby, the Church had been full to overflowing, and he had again the
wonderful feeling of being able to sway men's minds.

As he paced up and down in the moonlight, he lifted his eyes to the starlit sky
and cried to God to forgive all his past unsatisfactoriness and to make him
once more of use in the world.

As for Rachel she was in a dream of happiness. In fact it seemed as if life had
suddenly opened to her in all its rich fulness. The presence of her husband,
her child, the country air laden with all sorts of perfume; the feeling of rest and
quiet after the strain and stress of Trowsby; and the consciousness that she
was getting her strength back and had not to be always thinking of ways and
means, filled her with thankfulness. Moreover, she had a most faithful
nursemaid in Polly who she counted distinctly as one of her blessings. Polly's
devotion to Pat showed itself in many ways; and Rachel felt that she could
trust the child perfectly to her when she was feeling unable to make any effort
on his behalf. For though she knew she was gradually getting stronger she
was conscious that her amount of strength was at present very small and that
any unnecessary effort was bad for her.

"I am going to Trowsby," said Luke one morning. "I am not happy about my
mother. Her letters strike me as rather depressed."

"I am afraid that she must miss you very much," said Rachel.

"I fancy that is what is making her depressed. Anyhow I shall go and find out. I
shall rather like to be in Trowsby again," he added.

"You mustn't like it so much that you'll want to be back again," said Rachel.

Luke laughed. He would have given the world to be back again, but he did not
tell her so. Anyhow it would do him good just to have a look at the people. And
if he started quite early in the morning, by 7.30, he would have a long day
before he need return by the 8 o'clock train.

The streets of Trowsby did for him what the trees and flowers did for his wife.
He felt he could breathe again, and the depression that had weighed him
down rolled away. His first visit was to the church. It was empty. After kneeling
in prayer, he sat down and lived over again the Sundays he had spent there.
He remembered the crowded building, the earnest listeners, the hearty
singing, and compared it with his present village Church.

Then with a sigh he rose and made his way to his mother's rooms. That she
was missing him terribly, he saw at once.

"You must come and live with us," he said. "Why not?"

"My dear I could not do that," she answered. "If Rachel asked me that would
be another thing. But she is not likely to do that."

"But why not?" said Luke. "I am quite sure she would be delighted. I can't think
why the plan was not thought of before."

Mrs. Greville smiled.

"Have you ever come across a daughter-in-law who would welcome such an
idea? I haven't. No, it would not answer."

"Perhaps not with most people; but you are different. I can't imagine Rachel
not liking the suggestion. Of course she would be only too delighted."

Mrs. Greville shook her head. "It is impossible," she said. "I like Rachel and
admire her in many ways, but I am perfectly sure that our feelings for one
another would be strained and uncomfortable. I don't know if you are aware
she has never once called me mother. I am Mrs. Greville to her and nothing
more."

"What?" exclaimed Luke.

Mrs. Greville, seeing her son's astonishment, was sorry that she had
mentioned the fact to him.

"Oh it really does not signify," she hurried to say. "I daresay it has never struck
her. And I have not a word to say against her. She is a very nice girl and an
excellent wife. But you see the kind of footing we are on. She would not
welcome me I am quite sure."
"I am convinced that you are mistaken," said Luke. The idea had never
entered his mind, that his wife and mother were not on the closest of terms
with one another. His mother, he felt sure, was depressed from her late illness
and was looking at things through dark spectacles.

"You must put those ideas quite away from you," he said, "and you must come
and live with us. Wouldn't you like it?"

"I have never liked the thought of the country. But of course it would be far
less lonely and I suppose I could find enough to do in the village."

"Of course you would. You could start all sorts of things which Rachel is not in
a fit state to do."

"Well I shall not come unless I am definitely asked by your wife," said Mrs.
Greville, "as I am convinced that I should not be welcomed. Neither do I think
it at all wise for a mother-in-law to take up her abode with her son and his
wife. You will see that I am right."

Luke made the best of his time in Trowsby. He visited every member of his
men's Bible class; had tea with Mrs. Stone, looked up the district visitors and
finally found himself just in time to spring into the 8 o'clock train as it was
moving out of the station.

Meanwhile Rachel had had a lovely day in the garden. Little Pat was in his
perambulator by her side, crowing and happy. The birds were singing in the
trees above her. The gardener was cutting the grass in another part of the
garden with a scythe; that most delicious of all sounds; an occasional heavily
laden cart passed in the lane near by. She rejoiced in every sight, sound, and
smell, and the quiet and peace were as balm to her spirit.

When baby was taken away to be put to sleep for the night Rachel still lay on
under the trees, and was fast asleep herself when Luke opened the gate.

"Have you had a nice day?" she said, as she awoke at the sound of his
footstep. But she saw the question was unnecessary. His face was radiant.

"First-rate," he said, taking a seat by her side. "I enjoyed every minute of it."

"How is your mother?"

For the moment Luke had forgotten about his suggestion to his mother; and
the sudden remembrance of her words made him hesitate before answering;
then he said:

"Of course she misses me terribly. I don't feel happy at her being so far away."

He was so afraid of seeing by the expression on his wife's face that his mother
was right in her judgment, that he kept his eyes on the tree above him. Rachel
was silent. A sudden presentiment filled her mind and made her heart flutter.

Was Luke wanting his mother to live with them? Was it possible that such a
thought had entered his mind! How could she bear it? She had grown to like
Mrs. Greville, indeed to love her in a way.

Her devotion to little Pat was almost pathetic and had drawn them together.
But to have her in the house, for the peace to be interrupted by her restless
activities; to hear her loud voice disturbing the quiet of the home and garden!
How could she bear it! And yet—yes she was sure from the look on Luke's
face as he gazed up into the tree, that this was what he wanted to propose
and for some reason felt nervous of doing so. She was silent; then mastering
herself she said quietly:

"Of course she must miss you terribly. What a pity Trowsby is so far away."
With a fear lest he should then and there propose to her what she believed
would wreck the happiness and peace of the home, she added quickly, "I think
it is getting a little damp and chilly. Will you bring in my chair dear."

Luke was all concern in a moment. Rachel must not get cold. He folded up the
chair and followed her into the house. He was just a little surprised that Rachel
had not caught his thought. She was generally so quick at discovering his
meaning; but evidently the idea of his mother living with them had never
crossed her mind. He must try and broach the subject again later on. Had it
not been for his mother's words he would not have felt the slightest hesitation
in doing so; but what she had said was making him find it a little difficult for the
first time to tell Rachel his wish.

"What is the time?" asked Rachel as she paused at the door of the drawing-
room.

"Half past nine."

"Then I shall go straight to bed," she said. "Polly has laid your supper in the
dining-room. I must wait to hear all about your day till to-morrow, then I shall
be fresher."
On reaching her bedroom Rachel locked the door and sank into a chair. The
shock of the discovery of what was in Luke's mind made her feel quite faint.
Was her cup of happiness to be taken from her? She had so enjoyed having
her husband and child to herself—and so thankful that for a time, at least, the
subject of economy could be put on one side—that she need not worry any
more over eggs being 4d each or that margarine was cheaper than butter.
She hoped that she had left all that behind in Trowsby for ever; but she was
convinced that if Mrs. Greville lived with them the subject of economy would
continually crop up whether it were needful or not. Ways and means were too
interesting a topic to her mother-in-law to allow of her dropping it for long.

Then there were the servants. Polly had a rooted objection to Mrs. Greville,
and as for her new maid she was one who disliked any interference. Rachel
felt that she would certainly lose her, and if it were not for Polly's devotion to
little Pat and herself, there would have been small chance of keeping even
her. Anyhow the peace and the intense happiness would be gone. She would
feel that she had lost both husband and child. Mrs. Greville would dominate
them all and would rule the house. Rachel knew by this time, moreover, that
her ideas on the bringing up of children were in direct opposition to her own.

What should she do if Luke asked her outright to invite her mother-in-law to
live with them? Should she tell him of the difficulties which would certainly
arise? Would it be possible to talk them over together without hurting him too
much? But no. She knew that Luke would not in the least understand them. It
would only make matters worse. She must either put her foot down and say
decidedly that it could not be, or give way.

Rachel in her distress knew there was only one thing to do. Only one answer
to give. She must just pray for strength to do what she knew was her duty; and
to take up the cross without murmuring.

Luke was spared the ordeal he had begun to dread; for at breakfast the next
morning Rachel looked at him across the table with a smile.

"I have been thinking about your mother," she said. "Why not ask her to come
and live with us. Would she like it?"

Luke's whole face lit up.

"That is exactly what I should wish, dearest," he said. "But will it put more on
you? Happily we have Emma, and two servants ought to be able to work the
house well."
"Anyhow," said Rachel, "we might try the experiment."

"I'll write this morning," said Luke joyfully. "No, it would come better from you.
And Rachel," he said, with a little hesitation, "call her 'mother' will you? That
would bring her I know. She would feel we really wanted her."

Rachel laughed. Had she not laughed she would have cried.

"All right," she said. "You shall see my letter before it goes."

Luke was overjoyed. He was so glad that he had been right. There was
evidently no feeling whatever against his mother's coming in Rachel's
judgment. In fact she was evidently pleased at the suggestion. He would write
also and tell his mother that she had been quite wrong in imagining that his
wife would not like the plan.

Rachel dashed off her letter as quickly as she could lest her heart should fail
her, and showed it to Luke.

"Dear Mother," she wrote;

"Why not come and live with us? You would
like this place and would feel much less
lonely than living on in Trowsby. We do not
like to think of you there by yourself."
"Your affectionate daughter-in-law,"
"Rachel."

Rachel pointed to the beginning as Luke took it in his hands, saying, "I have
called her mother for love of you."