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Process Safety Calculations
Process Safety Calculations
Second Edition

Edited By
Renato Benintendi
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States
Copyright © 2021 Elsevier Ltd. All rights reserved.
No part of this publication may be reproduced or transmitted in any form or by any means, electronic or
mechanical, including photocopying, recording, or any information storage and retrieval system, without
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Publisher’s permissions policies and our arrangements with organizations such as the Copyright Clearance
Center and the Copyright Licensing Agency, can be found at our website: www.elsevier.com/permissions.
This book and the individual contributions contained in it are protected under copyright by the Publisher
(other than as may be noted herein).

Notices
Knowledge and best practice in this field are constantly changing. As new research and experience broaden our
understanding, changes in research methods, professional practices, or medical treatment may become
necessary.
Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using
any information, methods, compounds, or experiments described herein. In using such information or methods
they should be mindful of their own safety and the safety of others, including parties for whom they have a
professional responsibility.
To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability
for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or
from any use or operation of any methods, products, instructions, or ideas contained in the material herein.

Library of Congress Cataloging-in-Publication Data

A catalog record for this book is available from the Library of Congress
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library
ISBN: 978-0-12-823516-4

For information on all Elsevier publications

visit our website at https://www.elsevier.com/books-and-journals

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Author Biography
Renato Benintendi Msc CEng FIChemE is a senior researcher at Chemical Physical
Department, ULB University, Brussels and Process Safety and Loss Prevention Principal
Consultant at Wood (Formerly Foster Wheeler), Reading Office. He has authored more than
40 publications in international journals, is tutoring and mentoring dissertations in several
universities in the United Kingdom, France, and Italy. He has 35 years’ experience in process
engineering, process safety engineering, environmental engineering, asset integrity
management, is lecturing and delivering conference papers in United States, Asia, Europe, and
is the author of research programs in process safety and environmental engineering. His
specialties encompass process safety, safety modelling, HSE international regulation expertise,
environmental engineering, process engineering, and unit operation engineering.

xix
Preface to the Second Edition
The first edition of the book Process Safety Calculations has favourably been received by
teachers, researchers, students, and practitioners. Some universities have declaredly
appreciated the significant number of chapters dedicated to the chemical engineering
background, specifically oriented to the process safety subject. On the other hand, the large
coverage of the consequence assessment topics along with the constant support of numerous
practical examples has also been appreciated by colleagues and practitioners, engaged in
the complex world of process safety studies. Amazingly, Forbes has included this volume
among the 10 best thermodynamics books of all time, together with Enrico Fermi and Ilya
Prigogine. This outcome has encouraged the author to accept the kind invite of the editor to
prepare a second edition of the book. This has been fully revised, the calculations have been
checked and corrected, and five new chapters with new examples have been added. The
rationale of a second edition is the evidence that the multifaceted world of the quantitative risk
assessment is made of specific sessions, each of which entails the knowledge and the
practice of the related techniques and norms. Chapter 13 covers the dynamics of the buildings
subject to explosions, a subject with many technical and cost implications, typically shared by
process safety and civil engineers. The Layer of Protection Analysis, a technique adopted in
the functional safety framework, but also a powerful QRA tool, has been presented in
Chapter 14 with many applicative examples. In Chapter 15, the protective design criteria of
vessels and enclosures have been described, with the detail of the structural elements and the
comparison of the American and European norms. The complex and often misunderstood
scenario of toxicity has been presented in Chapter 16, with the aim to clarify the disciplinary
definitions with the contribution of the applicable regulations and with the aim to provide the
reader with the capability of untangling the various practical aspects of the topic. Lastly,
Chapter 17 covers the important subject of the integrity of the equipment exposed to external
fires, a theme which always presents a high level of uncertainty in the design and the safety
scenario. The second edition of the book has kept the nature of book of calculations of the
first edition, without compromising the necessary theoretical frame, being the author still
convinced that this approach will result useful and effective for a full understanding of the
discipline.
Reading (United Kingdom), February 2021

xxi
 CHAPTER 1

Chemistry of Process Safety

Nothing is lost, nothing is created. Everything is transformed.

(A. Lavoisier)

1.1 Stoichiometry and Mass Balances

Stoichiometry (from the ancient Greek στοιχε~ιον element and μέτρον measure) is a
fundamental part of basic chemistry that can be defined as the relationship between the relative
quantities of substances taking part in a reaction or forming a compound, typically a ratio of a
whole integer.
The stoichiometry of a chemical reaction can be expressed through the expression:
aA + bB + ⋯ ! cC + dD + ⋯ (1.1)
or
X
n X
m
ri Ri ! qj Qj (1.2)
1 1

where a, b and c, d are, respectively, the reactants and products reaction coefficients, and A, B,
C, and D are the atoms or the molecules involved in the reaction. Eq. (1.2) is a generalised form
of the same formula. It is worth noting that
ri
sij ¼ (1.3)
qj
is the stoichiometric ratio of Ri to Qj and indicates the constant relationship between the
concentrations of these chemical compounds throughout the reaction path.
Pure mixing and dispersion processes do not cause any modifications of the chemical identity of
the substances because of the physical nature of these phenomena.

Process Safety Calculations. https://doi.org/10.1016/B978-0-12-823516-4.00005-4

Copyright # 2021 Elsevier Ltd. All rights reserved.
3
4 Chapter 1

1.1.1 Mass Balances

Mass balances are broadly used in process engineering where process streams and
configurations are well defined. Instead, process safety scenarios are variable and often very
complex. Considering a portion of space (Fig. 1.1), the following general equation of mass
balance applies:
Wacc ¼ Win  Wout + Wgen (1.4)
where

– Win is the mass entering the space domain

– Wout is the mass leaving the space domain
– Wgen is the mass generated or converted
– Wacc is the mass inventory variation

According to Lavoiser’s principle, Wgen exists only for components which are transformed into
other components.
Process safety engineering entails a broad range of complex and variable scenarios where a full
understanding of stoichiometry and mass balances is necessary to properly analyse and assess
the related process and plant configurations. Some cases are discussed here, and specific
scenarios have been analysed in the next paragraphs.

1.1.2 Chemical Reactions

A low-pressure vessel contains a stoichiometric mixture of carbon monoxide and pure oxygen
at ambient temperature To (Fig. 1.2).
The system undergoes a chemical reaction that converts all carbon monoxide into carbon
dioxide and is assumed to be at thermal equilibrium so that the initial ambient temperature is
attained. Application of the ideal gas laws, with V and To constant, gives

Wout
Wgen
Win

Wacc

Fig. 1.1
Mass balance on a generic space domain.
 Chemistry of Process Safety 5

CO + 0.5 O2 CO2

CO O2 CO2
Po, To, V P1, To, V

Fig. 1.2
Oxidation of carbon monoxide leading to vessel depressurisation.

N1
P1 ¼ Po (1.5)
No
where N1 and No are the final and initial number of kilomoles of product and reactants,
respectively, which in this specific case coincides with the reaction stoichiometric coefficient
N1 1
srp ¼ ¼ ¼ 0:67 (1.6)
No 1:5
It can be concluded that the reaction, assuming an overall isothermal and isochoric condition,
causes a 33% pressure drop, which could result in a catastrophic outcome for the vessel.

1.1.3 Jet Flows From Pressurised Systems

Jet flows from pressurised containments are frequent in process safety. The consequences of
toxic or flammable compound dispersion strictly depend on jet dynamics. The scenario shown
in Fig. 1.3 illustrates the release of hydrogen sulphide from a pipeline.
The toxic gas is released with a mass flow rate WH2S. Air is entrained into the jet as long as this is
developed, resulting in a progressive dilution of H2S. Depending on the effect of the
entrainment, toxic concentrations are proportionally reduced, while flammability will be
promoted by air mixing within a specific region of the jet. Assuming a steady-state value of
WH2S, and indicating with WAIR(z) the air entrainment mass flow rate per length unit along z, the
mass balance at z ¼ h can be written as
ðh
W ðhÞ ¼ WH2 S + WAIR ðzÞdz (1.7)
0
6 Chapter 1

Air entrainment

H2S

Fig. 1.3
Release of hydrogen sulphide from a pipeline.

It has been shown how important is the correct management of this balance in jet flow
consequence assessment studies.

1.1.4 Flash Flow

A flash flow is the release of a liquid from a containment where the operating temperature is
significantly greater than its downstream boiling temperature, typically the normal boiling
temperature. The liquid is forced to vaporise a fraction of it to reach the downstream
equilibrium condition. This is the case of LPG stored at ambient temperature (Fig. 1.4).
The liquid mass W splits into the flashed vapour fraction XV and the liquid fraction XL. It is
W ¼ XV + XL (1.8)

1.1.5 Absorption and Adsorption

Removal of toxic or dangerous compounds can be accomplished via mass transfer units, such as
absorbers or adsorption towers. A typical example is the amine treatment of sour gas (Fig. 1.5),

Fig. 1.4
Flash flow from a pressurised containment.
 Chemistry of Process Safety 7

Sweet gas
Q, Sout

Lean amine
q
Sour gas Rich amine
Q, Sin q, Sam

Fig. 1.5
Amine treatment of sour gas.

or absorption of carbon dioxide with sodium hydroxide. For sour gas treatment, neglecting the
change of flow rates Q and q, the mass balance of H2S can be simplified considering the
concentration of sulphur S:
Q  Sin ¼ Q  Sout + q  Sam (1.9)

Example 1.1
How many kilograms of oxygen are required to enrich 500kg of air to 50% of O2 (molar basis)?
(Air molecular weight ¼ 29, oxygen molecular weight ¼ 32).
Solution
500 kg of air correspond to the following kilomoles:
500
Nair ¼ ¼ 17:24 (1.10)
29
500
NO2 ¼  0:21 ¼ 3:62 (1.11)
29
500
NN2 ¼  0:79 ¼ 13:62 (1.12)
29

The final amount of oxygen will be, as requested, the same as that of nitrogen, i.e. 13.62 kmol.
Therefore, the oxygen to be added can be calculated by difference:
ΔNO2 ¼ 13:62  3:62 ¼ 10 kmol ¼ 320 kg (1.13)
8 Chapter 1

WSO2
WH2S
WN2
WAIR
WO2

Fig. 1.6
H2S oxidiser.

Example 1.2
(a) A gas stream of hydrogen sulphide is sent to a burner that is fed with the necessary air to
oxidise the sulphide to sulphur dioxide. Knowing that the off gas contains 464.8 kg/h of
molecular nitrogen and 20.8kg/h of molecular oxygen, determine (a) The mass flow rate of
hydrogen sulphide sent to the burner
(b) The sulphide oxidation efficiency
(Hydrogen sulphide molecular weight ¼ 34, nitrogen molecular weight ¼ 28)
Solution
With reference to Fig. 1.6, the combustion process is represented by the following reaction:
0:79 0:79
2H2 S + 3O2 + 3  N2 ! 2SO2 + 2H2 O + 3  N2 (1.14)
0:21 0:21
Nitrogen does not participate in the reaction, so being the stoichiometric coefficient:
2
sH2 SN2 ¼ ¼ 0:177 (1.15)
0:79
3
0:21
and the nitrogen molar flow rate 468:4
28 ¼ 16.6 kmol/h, the hydrogen sulphide mass flow rate is
WH2 S ¼ 0:177  16:6  34 ¼ 100 kg=h (1.16)
Unreacted oxygen is 0.65 kmol/h. Oxygen fed to the burner is equal to 16:6  0:79 ¼ 4:4 kmol=h.
0:21

The conversion efficiency is calculated considering the ratio of unreacted to supplied oxygen:
0:65
ηH2 S ¼ 1  ¼ 0:85 (1.17)
4:4

Example 1.3
A storage tank contains a heavy hydrocarbon with a negligible vapour pressure at the operating
temperature. The tank is nitrogen blanketed so that a positive overpressure of Po is maintained.
The tank emptying is started with a head free volume of Vo and a liquid flow rate equal to Q. Find
 Chemistry of Process Safety 9

PIC

N2
PCV
Vo, Po

Fig. 1.7
Emptying of a nitrogen blanketed tank.

the nitrogen mass to be provided with time by the controller PIC in order to ensure that positive
overpressure Po is maintained during all emptying phases (Fig. 1.7).
Solution
The tank head space is assumed to be occupied by nitrogen only. Application of ideal gas laws:
P  V ¼ nN2  R  T (1.18)
Imposing that pressure is maintained constant by the PCV. It is
2 3
1
d
dP 6 1 dnN2 7
¼ R  T  4nN2   V +  5¼0 (1.19)
dt dt V dt

Simplifying and rearranging:

1 dV dnN2
nN2   ¼ (1.20)
V dt dt
Considering that dV
dt ¼ Q and that V ¼ V o + Q  t, Eq. (1.20) may be written as
1 1 dnN2
Q¼  (1.21)
Vo + Q  t nN2 dt
Separating
d ðVo + Q  t Þ dnN2
¼ (1.22)
Vo + Q  t nN 2
Solving
 
Vo + Q  t
WN2 ðtÞ ¼ 28  nN2 ðt Þ ¼ 28  nN2o  (1.23)
Vo
where nN2o is the molar nitrogen amount of Vo at t ¼ 0. This result is intuitive but has been
rigorously obtained here via the application of mass balances.
10 Chapter 1

1.2 States of Substances in Process Safety

Substances in process safety can be present in the following forms:

1.2.1 Gases and Vapours

Gas is a fundamental state of substances at a temperature higher than their critical temperature.
Hydrogen and methane have to be regarded as gases at ambient temperature, whereas propane
and sulphur dioxide are vapours and can be condensed by compression.

1.2.2 Liquids

Liquids are the condensed phase of vapours. They can be in equilibrium with their vapours at
any temperature, and vapour pressure is the equilibrium pressure exerted by vapour above the
liquids. Liquids can be miscible or immiscible, polar or non-polar, and this behaviour strongly
affects the release and dispersion scenarios.

1.2.3 Dusts

In addition to being combustible, dusts which are finely divided solid particles can be
explosive. According to BS-EN 60079-10-2 (2015), combustible dusts, 500 μm or less in
nominal size, may form an explosive mixture with air at atmospheric pressure and normal
temperatures. Particular types of solid particles, including fibres, are combustible flyings,
greater than 500 μm in nominal size, which may form an explosive mixture with air at
atmospheric pressure and normal temperatures (BS-EN 60079-10-2, 2015).
As for gases and vapour, the mechanism of dust explosion consists of the rapid release of heat
due to the chemical reaction:

Fuel + oxygen ! oxides + heat

Metal dusts can also exothermically react with nitrogen and carbon dioxide, according to
Eckhoff (2003), who classifies explosive dusts as follows:

– Natural organic matters

– Synthetic organic materials
– Coal and peat
– Metals such as aluminium, magnesium, zinc, and iron
 Chemistry of Process Safety 11

1.2.4 Hybrid Mixtures

A hybrid mixture is a combined mixture of a flammable gas or vapour with a combustible dust
or combustible flying, which can behave differently from the gas/vapour or dust individually
(BS-EN 60079-10-2, 2015).

1.2.5 Explosive Mists

Dispersed droplets of liquids which, in some situations, may form a flammable mist which may
then give rise to an explosion hazard. It has been proved that aerosol sized droplets (sub-micron
to 50μm) will likely be the most easily ignitable portion of the mist cloud (BS-EN 60079-10-
2, 2015).

1.2.6 Supercritical Fluids

The defined state of a compound, mixture, or element above its critical pressure and critical
temperature (IUPAC, 2014). Carbon dioxide in carbon capture and storage (CCS) processing is
frequently handled in its supercritical state.

1.3 Mass and Concentration Units in Process Safety

Mole
Amount of grams corresponding to the atomic or molecular weight of a substance.
K mole
Amount of kilograms corresponding to the atomic or molecular weight of a substance.
Molar fraction (gas and liquid phase)
Ni
xi ¼ (1.24)
ΣNi
where
xi is the molar fraction of component i
Ni is the number of moles or kilomoles of component i
Partial pressure (gas phase)
According to Dalton’s law, within the limit of validity of ideal gas laws:
pi ¼ yi  P (1.25)
where
yi is the molar fraction of component i in the gas phase
12 Chapter 1

pi is the pressure of component i

P is the total pressure

1.3.1 Partial Volumes (Gas Phase)

According to Amagat’s law, within the limit of validity of ideal gas laws:
Vi ¼ y i  V (1.26)
where

yi is the molar fraction of component i in the gas phase

Vi is the volume of component i
V is the total volume

1.3.2 Mass Fraction (Gas and Liquid Phase)

mi
xmi ¼ X (1.27)
mi

and
wi
xmi ¼ X (1.28)
wi

xmi ¼ mass fraction of component i.

where mi is the partial pressure of component i
wi is the mass flow rate of component i

1.3.3 Mass-to-Volume Concentration (Gas and Liquid Phase)

mi
ci ¼ (1.29)
V ðT Þ

where

ci is the mass-to-volume concentration of component i

V(T) is the system volume at temperature T
 Chemistry of Process Safety 13

Particular mass-to-volume concentrations are (gas phase):

mi
cNi ¼ (1.30)
VN ðT Þ
mi
cSi ¼ (1.31)
VS ðT Þ
where

cNi is the mass concentration at normal conditions

cSi is the mass concentration at standard conditions

Both states, normal and standard, are assumed in this book to be at 273.15 K and 1 atm,
according to Hougen et al. (1954). Under these conditions, the normal molar volumes are as
follows:
Volume of 1 mol ¼ 22:414L
Volume of 1 kmol ¼ 22:414m3

1.3.4 Parts per Million (Gas and Liquid Phase)

ppmw ðweightÞ  typical in liquids

mi
ppmw ¼ X  106 (1.32)
mi

If liquid is water, assuming water density as 1000 kg/m3 or 1000 g/L:

g mg
ppmw ¼ ¼ (1.33)
m3 L

1.3.5 Parts per Million (Gas Phase)

pi vi
ppmv ¼ yi  106 ¼  106 ¼  106 (1.34)
P V
where all symbols are known.

1.3.6 Molar Concentration (Aqueous Solutions)

It is denoted as [X] and indicates moles/litre.

14 Chapter 1

Table 1.1 Concentration units conversion summary

From To Multiply by
Molar fraction gas ppmv 106
ppmv Molar fraction gas 106
Molar fraction gas mg/Nm3 MW  1;000;000
22:414

mg/Nm3 Molar fraction gas 22:414

MW  1;000;000

mg/m3 Molar fraction gas 22:414  T

273:15  1;000;000  MW

Molar fraction gas mg/m3 273:15

22:414  T  1; 000;000  MW
3 MW
ppmv mg/Nm 22:414

mg/Nm3 ppmv 22:414

MW

ppmv mg/m3 273:15  MW

22:414  T

mg/m3 ppmv 22:414  T

MW  273:15
MW, molecular weight; T, temperature in K.

1.3.7 Concentration Units Conversion Summary

See Table 1.1.

Example 1.4
The IDLH (immediately dangerous to life and health) of sulphur sulphide is 100 ppmv. Calculate
it as mg/Nm3 and as a molar fraction. (MW  34).
Solution MW 3400
100 ppmv ¼ 100  ¼ ¼ 151:69 mg=Nm3 (1.35)
22:414 22:414
100
100 ppmv ¼ ¼ 0:0001 molar fraction (1.36)
1; 000; 000

Example 1.5
A pressure vessel contains:
10 kg of molecular nitrogen (MW  28)
20 kg of molecular oxygen (MW  32)
50 kg of carbon dioxide (MW  44)
Calculate molar and mass fractions at:
T ¼ 20°C and 1 atm.
T ¼ 60°C and 3 atm.
 Chemistry of Process Safety 15

Solution
Molar and mass fractions do not depend on pressure and temperature.
10
NN2 ¼ ¼ 0:36 kmol (1.37)
28
20
NO2 ¼ ¼ 0:625 kmol (1.38)
32
50
NCO2 ¼ ¼ 1:14 kmol (1.39)
44
0:36
xN 2 ¼ ¼ 0:17 (1.40)
0:36 + 0:625 + 1:14
0:625
xO2 ¼ ¼ 0:3 (1.41)
0:36 + 0:625 + 1:14
1:14
xCO2 ¼ ¼ 0:53 (1.42)
0:36 + 0:625 + 1:14
10
xmN2 ¼ ¼ 0:125 (1.43)
10 + 20 + 50
20
xmO2 ¼ ¼ 0:25 (1.44)
10 + 20 + 50
50
xmCO2 ¼ ¼ 0:625 (1.45)
10 + 20 + 50

1.4 Solutions and Chemical Equilibrium

A solution is defined as a homogeneous one-phase mixture of two or more substances. In
process safety, it is very frequent to deal with mixtures and solutions which may exist in any of
the three states of matter, gaseous, liquid, and solid. Knowledge of solutions and mixtures
chemistry is important to identify and calculate hazardous properties of the involved
substances.

1.4.1 Gaseous Solutions

Examples of gaseous solutions are mixtures of gaseous hydrocarbons, air that is mainly a
mixture of oxygen and nitrogen, off-gas from flaring, which typically contains carbon dioxide,
sulphur dioxide, water, and nitrogen. Non-reactive gas mixtures present a high degree of
homogeneity, so they can always be considered solutions. This is not always true for liquid and
solid mixtures. Gaseous mixtures are governed by Dalton’s law of partial pressures, which
states that the total pressure P of a mixture of n components i is equal to the sum of the partial
pressures Pi of all the different gases:
16 Chapter 1

X
n
P¼ pi (1.46)
1

pi ¼ P  y i (1.47)
where yi is the molar fraction of the component i.

Example 1.6
100kg of solid sulphur are burnt in a combustor at atmospheric pressure. Knowing that 10% of
air excess is used, find the partial pressure of nitrogen in the off-gas (sulphur molecular weight:
32, nitrogen: 28, oxygen: 32).
Solution
The combustion reaction is
79 79
S + O2 +  N2 ! SO2 +  N2 (1.48)
21 21
100kg of sulphur are equivalent to 3.125 kmol. From the reaction stoichiometry and considering
10% of air excess:

NSO2 ¼ 3:125 kmol (1.49)

NO2 ¼ 0:1  3:125 ¼ 0:3125 kmol (1.50)
79
NN2 ¼ 1:1  3:125  ¼ 12:93 kmol (1.51)
21
12:93
PN2 ¼ ¼ 0:79 atm (1.52)
12:93 + 3:125 + 0:3125

This result is intuitive, due to the equimolar S/O2 ratio.

1.4.2 Kinetics and Equilibrium in Gas Reactive Mixtures

The gas-phase reaction rate of the general chemical reaction presented in Eq. (1.2) may be written as
Y
n
rf ¼ kf  priRi (1.53)
1
where

rf is the forward reaction rate.

kf is the kinetic constant.
pRi are the reactant’s partial pressures.

Some reactions may be reversible; therefore, a similar equation may be written for the
backward reaction:
 Chemistry of Process Safety 17

Y
m
rb ¼ kb  pqi
Qi (1.54)
1

At equilibrium, the two reaction rates are the same:

rf ¼ rb (1.55)
and
Q
m
pqi
Qi
kf 1
KP ¼ ¼ Q (1.56)
kb n
priRi
1

where KP is the equilibrium constant.

Many important reactive mixtures in process safety reach the equilibrium.

1.4.3 Liquid Solutions

Liquid solutions are obtained by dissolving gaseous, liquid, or solid substances in liquids.
Depending on the nature and the behaviour of the dissolved substances (solute), and of the
liquid (solvent), a wide range of physical–chemical scenarios may be obtained, which have to
be well understood in order for them to be properly analysed process safety wise.

Liquid–liquid solutions
Miscible liquids form homogeneous solutions, whereas immiscible liquids form two-phase
dispersed emulsions. A general criterion used to establish whether or not two or more liquids
are miscible is comparing their polar features. The old saying like dissolves like is a very useful
rule of thumb. Therefore, polar species, such as water, have the ability to engage in hydrogen
bonding. Alcohols are less polar, but can form hydrogen bonding as well. Due to its strong
polarity, water is an excellent solvent for many ionic species. Non-polar species do not have a
permanent dipole, and therefore cannot form hydrogen bonding. Organic covalent liquids, such
as many hydrocarbons, fall within this category.
The following general criteria can be adopted to predict solubility of chemicals:

– Symmetric structure molecules have a very low dipole moment and are not dissolved by
water
– Molecules containing OdH and NdH can form hydrogen bonds
– Molecules containing fluorine and oxygen are expected to have a high dipole moment
– Pure hydrocarbons, oil and gasoline, are non-polar or weak molecules
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Should an American planter protest, the crop in one of his sugar or
tobacco fields was burned, nor was it long before the planter learned
that “irrepressible friends of Senor Vasquez had rebuked a grasping
foreigner.”
Should an American merchant protest at Vasquez’s charges,
something happened to the “impudent merchant’s” stores or
warehouses.
Yet Vasquez himself had always kept on the safe side of the law,
while cheerfully ruining Americans.
They were simply compelled to submit to his extortions. One
American, a planter, who had resolutely resisted the Spaniard, had
been found dead, but the crime could be fastened on no one.
Just before the outbreak of the Cuban rebellion, Henry Richardson
had started sugar plantations in the interior. He had fallen into
Vasquez’s hands at the outset, and had been systematically
plundered.
Hal Maynard, who had come to Cuba a year before as Mr.
Richardson’s private secretary, had detected the Spaniard in several
doubtful dealings.
Naturally Vasquez’s feeling for our hero was far from cordial.
While Hal and his employer were still in the interior, Vasquez had
tried to involve them in trouble with the Spanish authorities.
This menace Mr. Richardson had dodged by paying a liberal bribe to
the officer commanding the nearest garrison.
Nevertheless, more dangers threatened these two Americans.
Then Consul General Lee’s call had come for Americans to leave
Cuba. Mr. Richardson had gone the day before. Hal had lingered
long enough to collect two thousand dollars due his employer. This
accomplished, he had traveled hastily to Havana, meaning to leave
there on the historic ninth of April. We have seen how he had
reached there too late.
The money that Vasquez claimed as his due was the balance of an
exorbitant bill. He had already been paid far more than he was
entitled to.
But he had hoped to overtake and intimidate the American boy.
The carriage drew up before the hotel door, which appeared
deserted as, indeed, it was, for with money and food both scarce in
Havana, the hotels stand but a poor show of patronage.
“Your three fares, peon,” said Hal, dropping a few coins in the
driver’s hand.
“Four pesetas more,” insisted the driver.
Hal paid it, without protest, and disappeared inside. He was quickly
shown to a room, and requested that his trunk be sent up.
“Although I ordered that sent here from the interior,” he smiled, as he
bent over the box, “I expected to leave it behind.”
Unlocking the lid, he examined the articles in the trunk for some
moments, until a warning “Ss-sst!” reached his ear.
Rising quickly, Hal saw from whence the signal had come.
In the aperture made by an open skylight overhead appeared the
head of a dark-skinned young man.
His bright, restless eyes took in everything in the room, our hero
included.
“You are an American?” he asked, as Hal stepped under the skylight.
“Yes.”
“Then I am your friend. But have you an enemy?”
“I—I fear I have.”
“Look out of the window toward the harbor. Then come back.”
Hal quickly obeyed, returning with a perturbed face.
“You saw Senor Vasquez approaching, with two officers and a squad
of soldiers?”
“Just that!” affirmed Hal.
“The officers have a pretense, but Vasquez will really seek your
money. If you have it not with you, or know a safe hiding place, you
will fool him, but if the money is in your possession, it will surely be
taken from you.”
Hal hesitated, regarding the speaker with a look full of penetration.
What he saw was the frank, pleasing face of a youth of eighteen.
Somehow, Hal’s heart went out to the stranger.
“If,” said the other, “you have the money, and wish to save it, you can
trust it with me, senor.”
“What could you do with it?” projected Hal.
“Drop it into one of my pockets,” added the other, adding with a
laugh:
“No one would search such a thin, ragged Cuban as I for the
possession of so much money. But think quickly, senor, for Vasquez
will be here in another moment. Juan Ramirez is my name.”
“A Cuban?” asked Hal.
“See!” And Juan drew from a pocket what could easily become his
death-warrant—a small Cuban flag.
This he kissed with a simple, unaffected air of devotion.
“By Jove, I’ll trust you,” murmured Hal. “I’ve yet to meet a Cuban
thief!”
R-rip! In a second he began to unbutton his clothing, bringing out to
view from under his shirt a long, thin bag.
“This contains two thousand dollars,” he whispered.
“And if anything happens to you, to whom does the money belong?”
“Henry Richardson, at Key West.”
“He shall have it,” promised the Cuban. “Hush! There are steps on
the stairs.”
Like a flash, Ramirez vanished.
“Have I been duped?” wondered Hal, with a quick thrill of
apprehension.
Ramirez had looked like a fellow to be trusted. Yet, if Hal had kept
the money about him, it would soon pass into the hands of Vasquez,
who would be able to persuade the Spanish judges that his claim
was just.
“If Ramirez has stolen it,” quivered Hal, “all I can say is that I’d
sooner see him get it than Vasquez.”
Tramp! tramp! tramp! Reaching the head of the stairs, the soldiers
were now marching straight for his door.
Whack! thump! The door was thrown unceremoniously open, and the
uniforms of Spain filled the room.
 CHAPTER III.
“SPANISH EVIDENCE.”

“This is the young man?”

One of the two officers who appeared at the head of a file of a dozen
soldiers turned and put the question to Senor Vasquez.
That consummate liar responded by a nod of the head.
Though Hal Maynard had not studied his attitude, he stood at that
moment a typical young American.
With feet rather spread, his hands thrust into his trousers pockets,
shoulders manfully back and head inclining slightly forward, he
ignored Vasquez, but regarded the officers with a rather indolent look
in which there was just a trace of curiosity.
“A visitation, I presume?” he said, addressing one of the officers in
Spanish.
But the latter, barely looking at him, turned to the other officer to
command:
“Search the trunk.”
“It is locked,” said Hal, stepping slowly forward. “Permit me to offer
you the key.”
The officer who received it merely grunted, and immediately knelt
before the trunk.
Hal stood by looking on, until one of the soldiers, after scowling at
him an instant, darted forward and gave the boy a push.
“If I am in your way,” retorted Maynard, recovering his equilibrium,
“won’t you be kind enough to say so?”
“Silence!” ordered the commanding officer.
Hal responded by a polite nod.
“These officers don’t belong to the mob, and they should be
gentlemen,” he murmured. “If they’re not, it’s not for me to set them
the example.”
Flop! went a lot of Hal’s clothing, strewed promiscuously over the
floor.
Slap! followed his linen.
Smash! went a small hand mirror, flung across the room so that it
struck the wall and landed on the floor in atoms.
“May I ask a question, sir?” queried Hal, turning to the officer in
charge.
“Silence!”
“I beg your pardon,” went on Hal, imperturbably. “All I wanted to ask
was whether my property is to be ruthlessly destroyed before a
charge has been even made against me?”
“Silence!”
“If I had committed any breach of decorum in asking,” pursued Hal,
calmly, “please consider that I didn’t ask.”
“Silence!”
Thump! The butt of a soldier’s musket landed forcibly in Hal’s
stomach.
“Ouch!” grunted the boy.
“Silence!”
“Not even allowed to express natural emotion,” murmured our hero.
He couldn’t have talked much in his breathless condition, just then,
even if he wanted to.
He saw the soldier’s musket-butt aimed at him, and dodged as
nimbly as he could.
Click!
Another soldier cocked his weapon, aiming fully at the American’s
head.
At this the commanding officer smiled. Some of the soldiers laughed
softly. They wanted to see the Yankee flinch, and were sure that he
would—for had not their Havana newspapers told them that all the
Yankees were cowards?
But Hal, who felt reasonably sure that nothing short of violence on
his part would result in his death just then, did not feel inwardly
alarmed.
Instead, he slowly folded his arms, closed one eye, and with the
other squinted down the steel barrel that stared him in the face.
“Bah!” muttered he who had aimed, now raising the muzzle of his
piece. “The Yankee pig doesn’t even know what a gun is.”
“Silence!” came sharply from the commanding officer.
“Well,” murmured Hal, under his voice, “I am gratified to learn that
somebody else besides myself has to hold his tongue. I wouldn’t like
to do all the shutting-up!”
It was all a picnic, so he fancied, since he was not only sure that the
officers would find nothing compromising, but also sure that,
whoever got the money, Senor Vasquez would not.
But the Spaniard, who had been narrowly watching the boy, now
interposed:
“Captain, may a civilian subject suggest that the accused has not yet
been searched?”
“Senor,” replied the captain, bowing slightly, “your loyal suggestion
shall be at once acted upon. I myself will make the search.”
Thereupon the captain waved the soldiers away, most of them
withdrawing to the corridor and doorway.
“Stand beside the accused,” ordered the captain, nodding at two of
his men, who accordingly ranged themselves on either side of the
American.
“Senor,” said the captain, coldly, “you will understand that what I am
about to do is a duty imposed upon me.”
There was a trace of civility about this, which caused Hal to reply
politely:
“If it is your duty, captain, I would be the last one to urge you from it.
But I can tell you what I have about me. I have a pocket knife and a
sum of money.”
“Money?” uttered Vasquez, becoming alert at once. “It is mine—mine
by right!”
“You are mistaken,” replied Hal, coldly; “but if you need it you may
have it. I have only three pesetas.”
“Three pesetas?” faltered the Spanish merchant. He looked as angry
as a man who is being robbed, for three pesetas is but about sixty
cents.
“You may have it,” rejoined Hal, with mock generosity, “if the officer
permits me to present it to you.”
Then he threw his hands up while the captain went through his
pockets.
That officer looked a trifle ashamed of his task, for an army officer is
a gentleman, at least by education.
But Hal’s pockets, under the most rigid search, showed no more
than he had mentioned.
“Off with your clothes, senor,” came the next command.
Hal looked and felt a trifle surprised, but saw that the order was a
serious one.
“Shall I er—er—withdraw to the closet before disrobing?” he
suggested.
“Naturally not,” was the dry answer.
There was no help for it. Hal had to obey, which he did with the
poorest grace in the world.
But he passed through this ordeal like the others without mishap,
and was curtly informed that he could put on his clothing again.
This Hal did, next standing at ease between the two soldiers.
“Do you find anything?” asked the captain, turning to his subordinate.
“Nothing,” replied the lieutenant.
“A mare’s nest, eh?” smiled the captain, grimly.
Hal duplicated the smile, but in a more genial manner, then turned to
look at Vasquez.
But that Spaniard suddenly darted over to the trunk, knelt beside the
lieutenant, and began to help rummage among the few remaining
articles there.
“Ha! Here is something,” announced Vasquez, holding up a slip of
paper.
Hal looked on, wide-eyed, for he knew well that no such paper had
been among his possessions when he packed them.
Then he gave a gasp, for he realized the Spaniard’s game at last.
That scoundrel, by some clever legerdemain, had slipped a paper
among Maynard’s effects.
“Ho!” grunted the Spaniard, running his eyes over the page. “This is
a note, apparently, from one of the comrades of that bandit chief,
Gomez.”
He finished reading, while the captain stood looking calmly on.
“An American plotter!” screamed Vasquez. “This is proof conclusive
enough to merit for him a dozen deaths if that were possible!”
He held the page in one hand, pointing a denouncing finger at our
startled hero.
“Let me see it,” commanded the captain. “A letter relating to a
filibustering expedition, eh? This is, indeed, evidence. So!” turning to
Maynard. “You are one of the Yankees who help his majesty’s
subjects to rebel.”
“Upon my honor,” protested Hal, “I know nothing about that letter.”
“Your honor?” cried the captain. “Bah, you Yankee pig! Lieutenant,
bring him along under guard. To the Prefatura.”
To the Prefatura! To Havana’s police headquarters? Over the door of
that grim building might well be written, “All hope abandon, ye who
enter here!”
It was at the door of this building that all trace had been lost of
countless Cuban insurgents, the members of their families, and of
others who had in any way been suspected of sympathy with the
cause of the rebels.
From here, in the late hours of night, countless doomed ones had
been led away, ostensibly to imprisonment in Morro Castle or
Cabanas Fortress—with this horrible peculiarity, that they had never
reached their destinations or been heard from again!
To the Prefatura! For an instant, contemplating the letter which the
captain now held in his hand, Hal felt his heart sinking utterly.
“I was sure I could not be mistaken,” murmured Senor Vasquez,
softly.
That voice aroused the American as the bite of a snake would have
done.
“Senor Vasquez,” he cried, throwing his head back proudly, “we have
not seen the end of this matter!”
Then, bowing to the captain, Hal stepped between the two files of
soldiers as they formed.
Down the stairs they started. Vasquez brought up the rear, gnashing
his teeth.
He had found no trace of the money.
But perhaps he yet hoped to!
 CHAPTER IV.
AT THE PREFATURA.

Hal marched through the main entrance to the Prefatura.

His bearing was as proud as ever.
He could not have shown more fortitude had he felt that the whole
honor of Old Glory was resting on his youthful shoulders.
He had marched for more than two miles through the streets, his
military escort taking a roundabout course, as if they enjoyed
displaying this dangerous captive to the excited populace.
He had been jeered at, jibed at, made the butt of hundreds of coarse
jokes.
At last he had reached the Prefatura. Senor Vasquez still brought up
the rear. He carried himself with the air of one who wishes it
understood that he has done his duty by his country.
In the corridor of the Prefatura Hal’s escort halted until it could be
learned before which official the prisoner was to be taken.
In the same corridor were other prisoners, each under guard.
There was only this difference: Hal Maynard was erect, rosy, healthy-
looking. The other poor wretches, most of whom were women, were
plainly Cubans.
Their invariably starved appearance showed them to be
reconcentrados—people from the interior who had been driven in by
General Weyler’s infamous order, and then left to starve.
There was little, if any, acute terror in their fates. They had suffered
so much, had witnessed so many atrocities, that they were
indifferent to what was yet to come.
Paris, during the Reign of Terror, was not such a city of horrors as
Havana has lately been!
Captain Tamiva, Hal’s chief captor, still bearing the letter “found” in
the boy’s trunk, disappeared into one of the numerous offices
opening upon the corridor.
He soon came back, ordering the soldiers to take their prisoner in.
Hal found himself arraigned before a stern-looking, elderly Spaniard.
Before the latter, on his desk, lay the accusing letter.
He looked up quickly, this official, shot a penetrating look into the
boy’s face, and snarled out:
“So you are another of the Yankee pigs who root with our Cuban
sucklings!”
“I am an American citizen, certainly,” replied Hal.
“And a sympathizer, as I said.”
“I have never held communication with the insurgents.”
“But this letter?”
“I know nothing about it.”
“It was found in your trunk.”
“Though never placed there by me.”
“Bah! Of what avail is lying? Do you think you are talking to some of
your own stupid Yankees? Confess!”
“How can I,” retorted Hal, “when there is nothing to confess?”
The official scowled, snorting impatiently:
“Time is valuable. We have too many cases like yours to attend to.
The island is full of treason. Instantly tell me all you know about this
letter, and the plans at which it hints, or take the consequences.”
“There is nothing that I can tell you,” rejoined Hal, earnestly.
“Then take the consequences!”
“I shall have to, since I can’t run away from them.”
“Very well. Then this is the disposition of your case: At ten to-night
you shall be rowed across the harbor to Morro Castle. Once in a
dungeon there you will be out of my jurisdiction, and thenceforth
under the eye of General Blanco.”
All the while Senor Vasquez had stood by looking silently on with his
eager, burning eyes.
“One moment,” he now interposed. “May I have a word with the
prisoner.”
“To one of such known loyalty as Senor Vasquez,” replied the police
official, politely, “no favor can be refused.”
Vasquez led our hero to the other end of the room.
“You are to go to Morro Castle,” whispered the Spaniard, warningly.
“Do you know what that means?”
“Yes,” retorted Hal. “Solitary confinement until——”
“Until——” followed Vasquez, eagerly.
“Until American sailors and soldiers purify that loathsome place by
planting the American flag over it.”
“Fool!” hissed Vasquez. “Do you imagine you will ever reach Morro?”
“I know only what that official said.”
“Well, then, let me tell you,” snarled the Spaniard, “that you will only
embark in a boat that will start across the harbor. By and by that boat
will return without you, but you will never have reached Morro! You
will never be heard from again!”
“And it is for this you have plotted?” cried Hal, paling, but otherwise
keeping his composure.
“If I have plotted,” murmured Vasquez, rapidly, “it was for my own
good. You would not expect me to serve another than myself, would
you?”
“No!” came the answer, with withering sarcasm.
“Now, my young friend,” went on the plotter, dropping into a cooing
voice, “if I am a dangerous enemy, let us forget that. I am also a
good friend. Your employer owed me the money which you collected.
Put me in the way of finding that, and I have influence enough here
to secure your freedom.”
“Now, listen to me,” retorted Hal, spiritedly. “Whether my employer
owes you the money or not is nothing for me to decide. But I will tell
you this honestly: I don’t know where the money is, at this moment. If
I wanted to play into your hands, I simply couldn’t.”
“You are lying!” gnashed Vasquez, but a searching look into the
boy’s face soon convinced that shrewd judge of human nature that
Maynard spoke the truth.
“I am not going to waste more time on you,” went on the Spaniard,
passionately. “If you send for me before it is too late, I will come. As
you value even a few more days of life, don’t tempt fate by taking the
trip across the harbor to-night!”
Murmuring these words in the boy’s ears, the scoundrel turned to
dart way.
As he did so, another man moved forward, saying quietly:
“I will speak with the prisoner now.”
Hal did not know the speaker until Vasquez stammered:
“The British consul general!”
“Yes,” replied the visitor, Mr. Gollan, “I was informed that a British
subject named Maynard had been arrested. I hurried here only to
learn that Maynard is an American citizen. Is that the case?”
“It is, sir,” affirmed Hal.
“Still,” smiled Mr. Gollan, “perhaps I can do something. At the
request of my government, Consul General Lee turned over to me
this afternoon the papers and duties of his office. Mr. Maynard, can
you suggest any service that I can do you?”
“Now, I should say so!” vented overjoyed Hal. “I have been arrested
on false charges and a trumped-up paper. Can you not demand to
see that document?”
“Certainly,” replied Mr. Gollan. “Come with me.”
Together they stepped before the official who had just condemned
Hal to Morro Castle.
“Do you mind my looking at the letter on which this young man’s
arrest was ordered?” asked Mr. Gollan.
“Certainly not,” answered the official, at the same time raising the
paper from his desk and handing it over.
“Thank you.”
As Gollan ran his eyes over the paper, Hal stood looking on at the
spectacle that meant the turning point for his life or death.
Suddenly our hero started, uttered an exclamation of astonishment,
and snatched the paper from Mr. Gollan’s hands.
“I beg your pardon, sir,” came impetuously from the boy, “but do you
see this other side of the sheet? It is one of Vasquez’s own business
letter heads! He has blundered by not looking at the other side of the
sheet on which he wrote! It bears out my charge that he trumped up
this letter, for, bear in mind, sir, it was he who pretended to find it in
my trunk!”
“Car-r-r-r-ramba!” exploded Vasquez, first turning white, next
purpling with wrath.
Back went the paper into the police official’s hands.
Senor Vasquez tried to explain; the police official asked a half a
dozen questions in a breath, while Captain Tamiva had much to say.
But over all the hubbub arose Consul Gollan’s voice:
“As representative both of the interests of Great Britain and the
United States, I ask for the instant release of this prisoner.”
Too disconcerted to speak, the police official could only nod his
consent.
Hal felt an arm thrust through his. In a maze he was led down the
corridor and into the square.
Then a hearty voice said:
“My young friend, I am very glad to have served you. I would advise
you to leave Cuba at once.”
“I intend to,” responded Hal. “I saw an English brig loading at one of
the wharves. I think I will try to get passage on her.”
“The Emeline Atwood—a good vessel,” replied Mr. Gollan. “She is
bound, too, for Norfolk.”
Then, after much hand-shaking and many protestations of thanks
from Hal, he turned down one of the side streets to the water front.
The narrow thoroughfares appeared deserted. He walked quickly.
“Now, that was stupid of me,” muttered the boy, after going a quarter
of a mile. “Why didn’t I think to ask who it was that took word to Mr.
Gollan? Could it have been Ramirez?”
“Senor! senor!” whispered a voice through the shutters of a window.
“Walk faster, and remember that you are being followed!”
Like a shot Hal halted, trying to catch sight of his informant.
“No, don’t stop! Don’t look this way, or you’ll betray me,” came the
whisper. “But hurry! The deadliest danger hovers over you in the
next five minutes!”
Second Part.
 CHAPTER V.
“A SPANIARD OF HONOR!”

“Thanks!”
The acknowledgment, softly uttered as the warning, floated back
over Hal Maynard’s shoulder as he struck out on the double-quick for
the water front.
Once he turned. Over his shoulder he saw three indistinct figures
following him down the street.
Fast as he was traveling, the pursuers increased their speed until
they seemed likely to overtake him.
“Is this more of Vasquez’s deadly work?” groaned Hal. “Will he never
stop until he has destroyed me?”
Cold perspiration oozed out on the boy’s forehead.
He broke into a swift run.
At this gait, he calculated that less than three minutes would bring
him to the English brig’s wharf.
As he ran, he took a flying look over his shoulder.
Hardly more than two hundred feet to the rear were the pursuers,
their sandaled feet moving without noise.
“I can beat them,” thrilled Hal, putting on an even better spurt of
speed.
Just ahead was the water-front street.
Here, a swift turn to the right, and a speedy dash would carry him to
the wharf he sought.
Trip! Hal’s feet became entangled in something stretched across the
sidewalk.
He plunged, then fell to the sidewalk, measuring his full length there.
More quickly than he could rise, a figure darted out of the doorway.
Across the boy’s body a man hurled himself.
“You’ll fight for it—sure!” vented Hal, gripping the stranger by the
throat.
They grappled, struggled, breath coming quick and short.
Hal fought like a tiger. He quickly placed himself on top of his
assailant, but could not wrench himself loose.
Pit-patter-pat! Soft sandals struck the sidewalk as the three shadows
rushed upon the scene.
Not pausing an instant, they hurled themselves into the melee.
Many hands grappled the boy at once.
Maynard fought with renewed fury, but what could he do against so
many?
One seized him by either arm and shoulder, another grasped his
kicking feet.
“Help! help! help! Thieves!” roared the victim, but his captor-carriers
did not even attempt to stifle his cries—the surest way of proving that
they had no reason to fear interference.
Hal’s first assailant now darted back into the doorway, unlocking a
door, and making way for the squad to enter.
Still kicking and squirming, Hal Maynard was carried through the
house and out into a courtyard at the rear.
Here he renewed his shouts, with no other effect than to make his
captors smile maliciously.
At the rear of the yard a gate was unlocked.
Hal Maynard involuntarily crossed a second yard, after which those
who carried him entered another house.
Here he was carried into one of the rooms, and unceremoniously
dumped upon the floor.
“You stay there,” muttered he who appeared to be the spokesman,
“unless you are foolish enough to try to escape.”
“What would be the use?” grated Hal, inwardly. “They wouldn’t be so
sure of me if there was a dog’s chance to crawl out.”
The spokesman went out, but the other three remained.
Ting-a-ling-ling-ling! tinkled a bell in another room.
“A telephone,” conjectured Hal. “Will Senor Enrique Vasquez be at
the other end of the wire?”
Though he listened intently, he could not hear the words spoken into
the receiver.
Presently the fourth man came back.
As Hal had not made any effort to get up, his jailers now squatted
upon the floor, lighting paper cigarettes and puffing incessantly.
Minute after minute dragged by.
Hal did not address a word to his captors. Neither did he shout for
help, for he felt sure that he would not have been left ungagged had
they feared that his voice would reach friendly ears.
Nor did his captors speak, beyond an occasional word addressed to
one another.
“Whatever is to be done, they are merely the agents of some one
else,” cogitated Hal, his mind as busy as his tongue was idle.
“Vasquez bragged about his agents. Are these some of them? If so,
they are not a lot to boast about!”
His reflections were cut short by the sound of the wheels of an
arriving carriage.
Then steps sounded in a hallway, next at the door.
The door opened, to give entrance to Senor Vasquez, as Hal had
expected.
As the Spaniard’s burning gaze fell upon the boy, his face darkened,
though his lips smiled.