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Process Safety Calculations
Process Safety Calculations
Second Edition

Edited By
Renato Benintendi
Elsevier
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necessary.
Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using
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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
18 Chapter 1

Table 1.2 Dipole moment for some organic and inorganic substances
Substance Dipole Moment, Debyes Polarity
a
Ammonia 1.471 Polar
Hydrogen sulphide 0.97a Polar
Ethanol 1.69a Polar
Methanol 1.70a Polar
Ethane 0a Non-polar
Propane 0.084a Non-polar
Butane 0a Non-polar
Pentane 0a Non-polar
Hexane 0a Non-polar
Ethylene 1.109a Polar
Ethylene oxide 1.89a Non-polar
Phenol 0a Non-polar
Ethylbenzene 0.59a Polar
Benzene 0a Non-polar
Toluene 0.375a Non-polar
o-Xylene 0.62a Polar
m-Xylene 0.33a Non-polar
p-Xylene 0a Non-polar
Acetaldehyde 2.75a Ionic
Acetic acid 1.7a Polar
Diethanolamine 2.84a Ionic
Aniline 1.3a Polar
Pyridine 2.215a Ionic
Sulphur dioxide (g) 1.63a Polar
Sulphur trioxide 0a Non-polar
Hydrogen chloride 1.109a Polar
Carbon dioxide 0a Non-polar
Water 1.84b Ionic
Resins 2–3c Ionic
Crude oils < 0.7c Non-polar/polar
Asphaltenes 4–8c Ionic
a
Dean (1999).
b
Poling et al. (2001).
c
Riazi (2005).

A dipole moment gives just a very general indication of solubility of molecules. Table 1.2
includes the dipole moment for some organic and inorganic substances.
A common practice is to assume the following scale of polarity with respect to the dipole
moment:

– Dipole moment <0.4: Non-polar molecule. Behaviour equivalent to the homopolar

covalent bond.
 Chemistry of Process Safety 19

– 0.4 < Dipole moment <1.7: Polar molecule. Behaviour equivalent to the heteropolar
covalent bond.
– Dipole moment >1.7. Very polar (ionic) molecule.

Vapour–liquid equilibrium in liquid solutions

A liquid mixture may present toxic or flammable characteristics depending on the
concentrations of its components, both in the liquid and in the vapour phase. Therefore, it is
important to understand the behaviour of solutions in both phases. The most general
equilibrium relationship between vapour concentration and liquid concentration of a substance
in a mixture is given by the following equation:
y A ¼ KA  x A (1.57)
where yA and xA are the molar fraction in the vapour/gas phase and in the liquid phase,
respectively, and KA is the distribution coefficient. KA is an experimental datum, which depends
on system temperature and pressure. A simple but approximate relation to describe the liquid–
vapour equilibrium of a mixture is Raoult’s law, which states:
The partial pressure of solvent pA over a solution equals the product of the vapour pressure of
the pure solvent, PoA by the mole fraction of solvent, xA, in the solution.
pA ¼ PoA  xA (1.58)
and, according to Eq. (1.47), if yA is the vapour molar fraction and P the total pressure:
PoA  xA
yA ¼ (1.59)
P
The more dilute the solution (a high fraction of solvent typical of the so-called ideal solutions),
the more accurate is Raoult’s assumption.

Example 1.7
A mixture of n-butane and n-pentane is in equilibrium at 2atm and 30°C. Determine the liquid
and vapour composition (vapour pressures: n-butane ¼ 3.2 atm, n-pentane ¼ 0.78 atm).
Solution
Four equations are available with four unknown variables.
Pbo  xb 3:2
yb ¼ ¼  xb (1.60)
P 2
Ppo  xp 0:78
yp ¼ ¼  xp (1.61)
P 2
x b + xp ¼ 1 (1.62)
20 Chapter 1

yb + yp ¼ 1 (1.63)
Solving:
xb ¼ 0:504, xp ¼ 0:496, yb ¼ 0:806, yp ¼ 0:194 (1.64)
An empirical correlation to calculate KA for hydrocarbons and some inorganic gases is Hoffman’s
equation (Hoffman et al., 1953):
10ða + c  F Þ
KA ¼ (1.65)
P
where
 
1 1
F ¼b  (1.66)
TB T
a ¼ 0:0385 + 6:527  103 P + 3:155  105 P2 (1.67)
c ¼ 0:89  2:4656  103 P  7:36261  106 P2 (1.68)
and b and TB (normal boiling temperature) are included in Table 1.3.
For C7+ fractions, the following equations can be used:
γ ¼ 3:85 + 0:0135T + 0:02321P (1.69)
b7 + ¼ 562:78 + 180γ  2:364  γ 2
(1.70)
TB7 + ¼ 167:22 + 33:25γ  0:5394γ 2
(1.71)
Pressure is given in bars.

Table 1.3 Parameters of Hoffman’s equation

Substance b (K) TB (K)
Nitrogen 261.1 60.6
Carbon dioxide 362.2 107.8
Hydrogen sulphide 631.1 183.9
Methane 166.7 52.2
Ethane 636.1 168.3
Propane 999.4 231.1
i-Butane 1131.7 261.7
n-Butane 1196.1 272.8
i-Pentane 1315.6 301.1
n-Pentane 1377.8 309.4
i-Hexane (all) 1497.8 335.0
n-Hexane 1544.4 342.2
n-Heptane 1704.4 371.7
n-Octane 1852.8 398.9
n-Nonane 1994.4 423.9
n-Decane 2126.7 447.2
C6 (lumped) 1521.1 338.9
 Chemistry of Process Safety 21

1.4.4 Azeotropic Mixtures

Application of Raoult’s law shows that mixtures of vapour composition are generally different
from those of liquid composition, due to the different volatility (vapour pressures) of the
components. This is not always true, because some mixtures behave as a single pure compound
in correspondence to a specific composition and temperature at given pressures. Azeotropic
composition is found at concentrations where volatility is reversed, as shown in Fig. 1.8, that
represent the mixtures of two pure substances, A and B. In the left-hand zone, component A is
more volatile than component B, whereas in the right-hand zone it is the opposite. Therefore,
point Q in the liquid–vapour equilibrium zone corresponds to a liquid that is more rich in B and
to a vapour that is more rich in A than the original composition. For point P, it is the opposite. In
correspondence to the azeotropic composition, and to the azeotropic temperature, vapour will
have the same composition as liquid.
Table 1.4 includes some azeotropic mixtures with the indication of the azeotropic composition
(first component) of the azeotropic temperature at 1 atm.

Temperature

Vapour Vapour

Q P
Liquid

Azeotropic
temperature Liquid

Azeotrope

0% Azeotropic composition 100%

Composition component A

Fig. 1.8
Liquid boiling points and vapour condensation temperatures for minimum-boiling azeotrope
mixtures of components A and B.
22 Chapter 1

Table 1.4 Azeotropic mixtures at 1 atm (Dean, 1999)

1st Component 2nd Component Azeotropic Composition (%) Azeotropic Temperature (°C)
Hydrochloric acid Water 20.24 110
Sulphuric acid Water 98 338
Ethanol Water 78.1 95.5
Ethyl acetate Ethanol 71.8 69.2
Benzene Ethanol 68.2 67.6
Toluene Ethanol 76.7 32
n-Pentane Ethanol 34.2 95
n-Exane Ethanol 58.7 79

1.4.5 Gas–Liquid Equilibrium in Liquid Solutions

Solubility of gas in liquids increases with the gas partial pressure over the liquid phase. For
many gases, the relationship between the concentration of the dissolved gas and the partial
pressure over the liquid surface is expressed by Henry’s law:
yA
PA ¼ (1.72)
KH
Henry’s law is accurate at relatively low partial pressures and when the dissolved gas
concentration is not very high. Table 1.5 shows the inverse of Henry’s constants for some gases
in water.
Considering the frequent risk in the oil and gas and chemical industry, as well as in wastewater
management, and the very toxic effects of hydrogen sulphide, the following drawing is very
effective to understand the big risk of this substance, even in relatively low concentrations in
water (Fig. 1.9).

Table 1.5 Inverse of Henry’s constants for some gases in water (1/KH ×1024, atm/molar fraction)
T (°C) Air CO2 CO C2H6 H2 H2 S CH4 O2
0 4.32 0.0728 3.52 1.26 5.79 0.0268 2.24 2.55
10 5.49 0.104 4.42 1.89 6.36 0.0367 2.97 3.27
20 6.64 0.142 5.36 2.63 6.83 0.0483 3.76 4.01
30 7.71 0.186 6.20 3.42 7.29 0.0609 4.49 4.75
40 8.70 0.233 6.96 4.23 7.51 0.0745 5.20 5.35
50 9.46 0.283 7.61 5.00 7.65 0.0844 5.77 5.88
60 10.1 0.341 8.21 5.65 7.65 0.1030 6.26 6.29
70 10.5 8.45 6.23 7.61 0.1190 6.66 6.63
80 10.7 8.45 6.61 7.55 0.1350 6.82 6.87
90 10.8 8.46 6.87 7.51 0.1440 6.92 6.99
100 10.7 8.46 6.92 7.45 0.1480 7.01 7.01
International critical tables of numerical data, physics, chemistry and technology.
 Chemistry of Process Safety 23

0
6.
H2S in solution, mg/L

0
1800

5.
1600 At one atmosphere

4.0

H2S concentration in air (ppm)

1400

1200
3.0
1000

800
2.0

600

400 1.0

200 0.5

0
0 10 20 30 40
Temperature (°C)

Fig. 1.9
Gas–liquid concentration of hydrogen sulphide in water (US EPA, 1985).

Example 1.8
A vessel with wastewater which contains 10 ppm (weight) of hydrogen sulphide at 30°C. The
vessel is located below grade and is regularly accessed by a maintenance team through a ladder.
Engineers inquired about the necessity of installing some gas detectors in the confined space and
possibly to classify the zone as a restricted area. The very low sulphide concentration in the water
convinces the team not to take into consideration the detection system (Fig. 1.10).

H2S 10 ppmw

Fig. 1.10
Sour water vessel of Example 1.8.
24 Chapter 1

10 mg H2 S 10=ð34; 000Þ mol H2 S

Solution yA ¼ 10 ppm ¼ ffi ¼ 5:4  106 (1.73)
1 kg water 55 mol H2 O
yA
PA ¼ ¼ 609  5:4  106 ¼ 0:0032886 atm ¼ 3288:6 ppmv (1.74)
KH
The assumption made is wrong. This concentration kills immediately (OSHA, 2016) (end of the
example, please return to normal font).

Table 1.6 Solubility of hydrogen sulphide in organic solvents

Solubility
Solvent Molar Fraction % Mass
n-Pentane 0.0507 2460
n-Hexane 0.0537 2.195
n-Heptane 0.0541 1.910
n-Octane 0.0556 1.726
n-Nonane 0.0575 1.595
n-Decane 0.0587 1.471
Ethanol 0.0177 1.314
Phenol 0.0200 0.773
Pyridine 0.0934 4.246
Benzene 0.0561 2.520
Toluene 0.0663 2.560
o-Xylene 0.0698 2.350

1000
40°C
900
20°C
800
10°C
Partial pressure H2S (mm Hg)

700

600

500

400

300

200

100

0
0 0.01 0.02 0.03 0.04 0.05 0.06
Molar fraction H2S

Fig. 1.11
Partial pressure vs molar fraction of H2S in cyclohexane.
 Chemistry of Process Safety 25

Solubility data of hydrogen sulphide in hydrocarbon and derived organic solvents are included in
Table 1.6 (Groysman, 2014).
Solubility data of H2S in cyclohexane and n-decane at different molar fraction ranges are
presented in Figs. 1.11 and 1.12, respectively (reproduced from Gerrard, 1980).
These data can be considered approximately as representative of hydrogen sulphide solubility in
hydrocarbons, given the comparability of the molar fraction in Table 1.6.

70
93.3°C
60
71.1°C
Partial pressure H2S (atm)

50

40

30
37.7°C

20
4.4°C
10

0
0 0.2 0.4 0.6 0.8 1 1.2
Molar fraction H2S

Fig. 1.12
Partial pressure vs molar fraction of H2S in n-decane.

1200

1000
Partial pressure NH3 (mmHg)

20°C 10°C 0°C

60°C 50°C
800
40°C 30°C

600

400

200

0
0 20 40 60 80 100 120
Parts of NH3 in 100 parts of water (mass)

Fig. 1.13
Solubility values for NH3 in water (Sherwood, 1925).
26 Chapter 1

For some very soluble gases, such as sulphur dioxide and ammonia, Henry’s constant is very low,
so the respective solutions are away from the ideal, and more accurate data are necessary, as
reported in Figs. 1.13 and 1.14.
The inverse of Henry’s constants (bars per mole fraction) for light hydrocarbon gases (methane,
ethane, propane, n-butane, and i-butane) in water at various temperatures (Kelvin) may be
calculated according to the following equations (Riazi, 2005):
 
A3
A1 + A2  T + + A4  lnT
KH ¼ e T (1.75)
Coefficient A1 to A4 and applicable temperature and pressure ranges have been included in Table 1.7.
The average absolute deviation percentage associated with Eq. (1.75) falls within the range 3.6–7.5.

800
10°C
30°C 20°C
700 40°C
Partial pressure SO2 (mmHg)

600 0°C
15°C
500
50°C
400

300

200

100

0
0 5 10 15 20 25
Parts of SO2 in 100 parts of water (mass)

Fig. 1.14
Solubility values for SO2 in water (Sherwood, 1925).

Table 1.7 Henry’s constants for light hydrocarbons in water (API Technical Data Book, 1997)
T
Range Pressure
Hydrocarbon (K) Range (bar) A1 A2 A3 A4
Methane 274– 1–31 569.29 0.107035 19,537 92.17
444
Ethane 279– 1–28 109.42 0.023090 8006.3 11.467
444
Propane 278– 1–28 1114.68 0.205942 39,162.2 181.505
428
n-Butane 277– 1–28 182.41 0.018160 11,418.06 22.455
444
i-Butane 278– 1–10 1731.13 0.429534 52,318.06 293.567
378
 Chemistry of Process Safety 27

0.005
0.0045
0.004

Cl2 KH, molar fraction/atm

0.0035
0.003
0.0025
0.002
0.0015
0.001
0.0005
0
0 20 40 60 80 100 120
Temperature (°C)

Fig. 1.15
Henry’s constant for chlorine. Reproduced from data included in Lange, N.A., 1949. Lange’s Handbook of
Chemistry, seventh ed. Handbook Publishers, Sandusky, OH.

400

350

300
HCl (g/L water)

250

200

150

100

50

0
0 1000 2000 3000 4000 5000 6000
HCl (ppm in air)

Fig. 1.16
Solubility of hydrogen chloride in water (Wight Washburn, 1929).

In Fig. 1.15, Henry’s constant of chlorine has been reproduced between 0°C and 100°C
(Lange, 1949).
Hydrogen chloride solubility in water is high, as shown in Fig. 1.16.
28 Chapter 1

1.4.6 Gas–Liquid Equilibrium in Acid Gas Removal (AGR) Units

Sour gases such as hydrogen sulphide and carbon dioxide are removed via amine absorption
with chemical reaction. Gas–liquid equilibrium in this case does not follow Henry’s law due to
the high absorption promoted by kinetics. Figs. 1.17 and 1.18 present a graphical plot of the
experimental values provided by Barreau et al. (2006) relevant to the partial pressure of carbon
dioxide and hydrogen sulphide against gas mole up to 25wt% diethanolamine (DEA) mole ratio
at given temperatures.
Mole fraction solubility of hydrogen sulphide in straight chain alkanes at 298.15K, and a partial
pressure of 1.013bar can be approximated adopting the following equation, obtained from the
experimental work of Makranczy et al. (1976):
100  xH2 S ¼ 0:129  n + 3:584 (1.76)
where n is the no. of carbon atoms between 4 and 16.

1.4.7 Equilibria in Aqueous Solution

Pure water contains very low concentrations of hydronium (H3O+) and hydroxide ions (OH)
produced by water dissociation. At 24°C, the ion-product constant for water is (moles2/litre2):
KW ¼ ½H3 O +   ½OH  ¼ 1014 (1.77)
pH ¼ log 10 ½H +  (1.78)

0.9

0.8
Partial pressure CO2 (MPa)

0.7

0.6

0.5

0.4

0.3

0.2
DEA 25% wt T = 338.5 K
0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
mol of CO2 / mol of DEA

Fig. 1.17
Carbon dioxide solubility data in Diethanolamine (Barreau et al., 2006).
 Chemistry of Process Safety 29

0.4

0.35

Partial pressure H2S (MPa)

0.3

0.25

0.2

0.15
DEA 25% wt T = 339 K
0.1

0.05

0
0 0.2 0.4 0.6 0.8 1 1.2
mol of H2S / mol of DEA

Fig. 1.18
Hydrogen sulphide solubility data in Diethanolamine (Barreau et al., 2006).

where the symbols [] indicate the moles/litre concentration unit. Strong electrolytes such as
sulphuric acid and sodium hydroxide completely dissociate in a water solution, whereas weak
electrolytes, such as hydrogen sulphide and ammonia, partially ionise in water.

1.4.8 Hydrogen Sulphide

Hydrogen sulphide is a colourless gas easily soluble in water, where it dissociates as a diprotic
acid according to the equilibrium reactions:
H2 S>HS + H + (1.79)
HS + H2 O>S + H3 O + (1.80)
and the equilibrium constants are (Treadwell, 1960)

½HS   ½H + 
K1H2 S ¼ ¼ 9:1  108 (1.81)
½H2 S

½S¼   ½H + 
K2H2 S ¼ ¼ 1015 (1.82)
½HS 

Comparing the two constants, we see that the variation of HS and H+ due to the second
reaction is negligible, so their values in Eq. (1.81) can be considered equal and approximately:

½S¼  ¼ K2H2 S ¼ 1015 (1.83)

30 Chapter 1

Multiplying Eqs. (1.81) and (1.82):

K1H2 S  K2H2 S ¼ 9:1  1023 (1.84)

Example 1.9
Sour water contains 0.17kg/L of overall ionised and non-ionised hydrogen sulphide. Air is to be
blown through the liquid in order to strip out an amount equal to 1% of the overall acid.
Calculate the initial and the final pH.
Solution
½HS   ½H +  x2 x2
K1H2 S ¼ ¼ ¼ ¼ 9:1  108 (1.85)
½H2 S  ½HS  170=34  x 5  x
Since [HS] ≪ [H2S]:
x2 x2
ffi ¼ 9:1  108 (1.86)
5x 5
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
xo ¼ ½H + o ¼ 5  9:1  108 ¼ 0:000675 (1.87)
pHo ¼  log 10 0:000675 ¼ 3:17 (1.88)
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
x1 ¼ ½H + 1 ¼ 0:05  9:1  108 ¼ 0:0000675 (1.89)

pHf ¼  log 10 0:0000675 ¼ 4:17 (1.90)

The assumption to consider all dissociated H2S as HS and H+ can be generalised for other
substances, provided the dissociation constant is smaller than 104.

1.4.9 Sulphuric and Sulphurous Acid

Sulphur trioxide and dioxide are absorbed in water, producing, respectively, sulphuric and
sulphurous acid. Sulphur dioxide is the main outcome of the combustion of sulphur compounds,
even if a small amount of trioxide is formed, especially if a catalytic action is promoted by some
metals, such as vanadium. Sulphuric acid may be considered totally dissociated into hydrogen
and sulphate ions. Sulphurous acid is weaker and presents the following equilibria in water:
H2 SO3 >HSO3  + H + (1.91)
HSO3  >SO3 ¼ + H + (1.92)
with the following equilibrium constant (Treadwell, 1960):
½HSO3    ½H + 
K1H2 SO3 ¼ ¼ 1:7  102 (1.93)
½H2 SO3 
½SO3 ¼   ½H + 
K2H2 SO3 ¼ ¼ 5:0  106 (1.94)
½HSO3  
 Chemistry of Process Safety 31

1.4.10 Carbon Dioxide

In an aqueous solution, carbon dioxide is present as molecular CO2 along with strong diprotic
carbonic acid H2CO3 which is in equilibrium with its ionic species (a, Housecroft and Sharpe,
2008), (b, Treadwell, 1960)
CO2 + H2 O>H2 CO3 (1.95)
H2 CO3 >H + + HCO3  (1.96)
HCO3  >H + + CO3 ¼ (1.97)
with
½H2 CO3 
K1CO2 ¼ ¼ 1:7  103 (1.98)
½CO2 
½HCO3  ½H + 
K2CO2 ¼ ¼ 3  107 (1.99)
½H2 CO3 
½CO3 ¼ ½H + 
K3CO2 ¼ ¼ 5  1011 (1.100)
½HCO3  

Example 1.10
pH of carbonated water at 24°C is 5. Find the carbon dioxide pressure above the liquid surface.
Solution
Assuming all dissociated carbonic acid:

½HCO3  ½H +  ð105 Þ

2
ffi ¼ 3  107 (1.101)
½H2 CO3  ½H2 CO3 
½H2 CO3  ¼ 3:3  104 (1.102)
½H2 CO3  0:00033
¼ ¼ 1:7  103 (1.103)
½CO2  ½CO2 
mol
½CO2  ¼ 0:194 ffi 0:0035 molarfraction (1.104)
L
Applying Henry’s law:
yA
PA ¼ (1.105)
KH
And assuming from Table 1.5 K
H ffi 0.142  10 atm/molar faction:
1 4

PA ¼ 0:0035  0:142  104 ¼ 4:96 atm (1.106)

This result is consistent with data reported in the literature (Carroll et al., 1991) (Fig. 1.19).
32 Chapter 1

Fig. 1.19
Solubility of carbon dioxide with pressure in water at various temperatures (Carroll et al., 1991).

1.4.11 Ammonia

Ammonia is a colourless gas easily soluble in water, where it dissociates according to the
equilibrium reaction:
NH3 + H2 O>NH4 + + OH (1.107)
and the equilibrium constant is (Treadwell, 1960):

½NH4 +   ½OH 
KNH3 ¼ ¼ 1:8  105 (1.108)
½NH3 

1.4.12 Chlorine

Chlorine is a green gas with an irritating odour. It is easily absorbed by water and undergoes the
following reaction:
Cl2 + H2 O>H + + OCl + HCl (1.109)
with (Treadwell, 1960)
½H +   ½Cl   ½HClO
KCl2 ¼ ¼ 3:0  104 (1.110)
½Cl2 
 Chemistry of Process Safety 33

Hydrogen chloride and molecular chlorine are in equilibrium with steam and oxygen according
to Deacon’s reaction:
2HCl + 0:5O2 >H2 O + Cl2 (1.111)
This equilibrium is described by the equilibrium constant:
pH2 O  pCl2
KP ¼ (1.112)
p2HCl  pO
0:5
2

where KP (atm1/2) is defined as (Niessen, 2010) and T is in K:

 
4 7087
KP ¼ exp 8:244 + 1:512  10 T + (1.113)
T

Example 1.11
The PENEX process is used to isomerise naphtha. The feedstock is sent to two reactors, which are
charged with a catalyst activated by hydrogen chloride. A stabiliser column separates isomerate
from overhead vapours, which are sent to a scrubber where hydrogen chloride is removed
(Fig. 1.20). On the overhead line, a pressure relief valve is connected to the flare. Analyse the
operational scenario relevant to the PRV venting into the atmosphere and discuss the findings.
Solution
It is assumed that flare combustion is not affected by air humidity, which is a realistic
assumption. On this basis, steam partial pressure in the equilibrium equation may be considered

To the flare

To the scrubber

Feed

Stabilizer

Isomerate

Fig. 1.20
Penex stabiliser.
34 Chapter 1

120
N Cl2
× 100
N HCl + N Cl2 PO2=0.11 atm
100

PO2=0.01 atm
80

60

PO2=0.05 atm
40

20

0
0 200 400 600 800 1000 1200 1400 1600

Temperature, K

Fig. 1.21
Molecular chlorine fraction over chlorine content in the Deacon equilibrium.

equal to the molecular chlorine partial pressure (Fig. 1.21 modified, please check and replace).
Accordingly:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 
NCl2 pCl2 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
0:5  8:244 + 1:512  104  T + 7087
¼ ¼ PO2  KP ¼ PO
0:5 (1.114)
NHCL PHCl 2
T

As per the U.S. EPA (n.d.), the flare discharge temperature is between 500°C and 1100°C (773,
15 and 1373.15K). It is determined that the chlorine-based molar fraction of molecular chlorine
falls in the range 40%–57% and 6.5%–14%, depending on temperature and oxygen partial
pressure. It is also seen that temperature affects equilibrium much more than oxygen partial
pressure. This process segment is not safeguarded by a scrubber on the pressure relief valve line.
Hydrogen chloride IDLH is 50 ppm, while chlorine IDLH is 10 ppm.

1.4.13 Hydrolysis

Salts produced from weak acids, weak bases, or both undergo hydrolysis. Solutions of sulphides
and ammonium salts hydrolyse when dissolved in water. Ammonium salts undergo the
following hydrolysis reaction:
NH4 + + H2 O>NH3  + H3 O + (1.115)
 Chemistry of Process Safety 35

Table 1.8 Equilibrium constants for acids and bases in water solutionsa
Substance Formula Ka Kb
5
Acetic acid CH3COOH 1.8  10
Ammonia NH3 1.8  105
Aniline C6H5NH2 4.6  1010
Benzoic acid C6H5OOH 6.4  105
Boric acid HBO2 6.5  1010
Carbonic acid CO2 ! H2CO3b 1.7  103
H2CO3 ! HCO3 3.5  107
HCO 3 ! CO3
]
5.0  1011
Chromic acid H2CrO4 ! HCrO 4 1.8  101
HCrO 4 ! CrO4
]
4.0  07
Diethylamine (C2H5)2NH 1.3  103
Dimethylamine (CH3)2NH 7.4  104
Ethylamine C2H5NH 6.0  104
Hydrazine NH2NH2 8.0  07
Hydrofluoric acid HF 7.5  104
Hydroxylamine NH2OH 1.0108
8
Hypochlorous acid HClO 5.0  10
Formic acid HCOOH 2.0  104
Methylamine CH3NH2 5.0  104
Nitrous acid HNO2 4.0  104
Phosphoric acid H3PO4 ! H2PO 4 7.5  103
H2PO 4 ! HPO4
]
6.2  108
≡
HPO] 4 ! PO4 1.0  1013
Phenol C6H5OH 1.3  1010
Pyridine C6H5N 1.4  109
Sulphidric acid H2S ! HS 9.1  10 8

HS ! S] 1.2  1015

Sulphurous acid H2SO3 ! HSO 3 1.7  102
HSO 3 ! SO
]
5.0  106
a
Treadwell (1960).
b
Housecroft and Sharpe (2008).

and the equilibrium constant is the hydrolysis constant:

½NH3   ½H3 O + 
KiNH4 + ¼ ¼ 5:67  1010 (1.116)
½NH4 + 
Table 1.8 provides the equilibrium constants of some acids and bases (Treadwell, 1960).

1.5 Absorption and Adsorption

Toxic and flammable substances have to be removed from process streams either as part of the
process or to reduce the health and environmental impact. For this purpose, they are absorbed
by a liquid solution or adsorbed on porous media.
36 Chapter 1

1.5.1 Absorption With Chemical Reaction

Absorption is the transfer of a gas or a vapour to a liquid. This process depends on the driving
force existing between the liquid phase and the gas phase and is governed and limited by the
gas–liquid equilibrium condition and, in turn, by the gas solubility. The lower the dissolved gas
concentration, the greater is the mass transfer. This is the reason why absorption is promoted by
chemical reactions occurring in the liquid body between gas A and reactant B, which reduces
the concentration as gas is transferred to the liquid and is converted to D:
Aðgas ! liqÞ + BðliqÞ ! DðliqÞ (1.117)
In Fig. 1.22, p is partial pressure of A and C is concentration of reactant B in the liquid.
Applying Eq. (1.4) and assuming a steady state, the following overall and individual mass
balance can be written as (Table 1.9)
Win  Wout ¼ 0 (1.118)
WAin  WAout  WAgen ¼ 0 (1.119)
WBin  WBout  WBgen ¼ 0 (1.120)
WDout ¼ WDgen ¼ WAgen + WBgen (1.121)

1.5.2 Stripping

The operation of removing absorbed solutes from liquids is called stripping. This works
according to the same principles of absorption, but just inverts the driving force with the aim of

Low PA High CB

High PA Low CB

Fig. 1.22
Absorption with chemical reaction of gas or vapour A and liquid reactant B.
 Chemistry of Process Safety 37

Table 1.9 Absorption of gases and vapours with selected reagents (Teller, 1960)
Gas Reagent
Carbon dioxide Carbonates
Carbon dioxide Hydroxides
Carbon dioxide Amines
Carbon monoxide Cuprous amine complexes
Carbon monoxide Cuprous ammonium chloride
Sulphur dioxide Calcium hydroxide
Sulphur dioxide Potassium hydroxide
Sulphur dioxide Ozone—Water
Chlorine Water
Chlorine Ferrous chloride
Hydrogen sulphide Amine
Hydrogen sulphide Ferric hydroxide
Sulphur trioxide Sulphuric acid
Ethylene Potassium hydroxide
Ethylene Trialkyl phosphates
Olephins Cuprous amine complexes
Nitrogen monoxide Ferrous sulphate
Nitrogen monoxide Calcium hydroxide
Nitrogen monoxide Sulphuric acid
Nitrogen monoxide Water
Elaborated from Teller, A.J., 1960. Absorption With Chemical Reaction. Chem. Eng. 67, 111–124.

enhancing the gas transfer from the liquid to the gas stream. Unlike absorption, stripping is
promoted by high temperatures and low pressures. Stripping typically removes toxic or
hazardous gases such as hydrogen sulphides and ammonia.

1.5.3 Adsorption

Adsorption from the gas phase is a mass transfer process of a gas or a vapour to a solid. When
the molecules of the fluid come in contact with the adsorbent, equilibrium is established
between the adsorbed gas or vapour and the fluid remaining in the gas phase. For a given
adsorbate at a given temperature, an isotherm can be constructed, relating the mass of adsorbate
per unit of weight of the adsorbent to the partial pressure of the adsorbate in the gas phase. The
isotherm can be described by empirical equations such as Freundlich, Languimur or Brunauer,
Emmett, and Teller’s equations. Freundlich’s equation is
w ¼ k  pm (1.122)
where w is the mass of adsorbate per unit of weight of adsorbent, k and m are experimental
constants, p is the partial pressure. A family of adsorption isotherms having the shape typical of
adsorption on activated carbon is plotted in Fig. 1.23 (US EPA, 2002). These, along with other
38 Chapter 1

T1

Equilibrium adsorptivity (lb adsorbate/lb adsorbent)

T2

T3

T4

(Note: T1<T2<T3<T4)

Adsorbate partial pressure (psia)

Fig. 1.23
Type I adsorption isotherms for hypothetical adsorbate (US EPA, 2002).

isotherms whose shapes are convex upward throughout, are designated Type I isotherms. The
Freundlich isotherm, which can be fit to a portion of a Type I curve, is commonly used in
industrial design.
Table 1.10 presents Freundlich’s parameters for some organic compounds (US EPA, 2002).

Table 1.10 Parameters for selected adsorption isotherms (US EPA, 2002)
Isotherm Parameters
Adsorbate Adsorption Temperature (°F) k m Range of Isotherm
Benzene 77 0.597 0.176 0.0001–0.005
Chlorobenzene 77 1.05 0.188 0.0001–0.01
Cychloexane 100 0.505 0.210 0.0001–0.05
Dichloroethane 77 0.976 0.281 0.0001–0.04
Phenol 104 0.855 0.153 0.0001–0.03
Trichloroethane 77 1.06 0.161 0.0001–0.04
Vinyl chloride 100 0.200 0.477 0.0001–0.05
m-Xylene 77 0.708 0.113 0.0001–0.001
77 0.527 0.0703 0.0001–0.05
Acrylonitrile 100 0.935 0.424 0.0001–0.015
Acetone 100 0.412 0.389 0.0001–0.05
Toluene 77 0.551 0.110 0.0001–0.05
 Chemistry of Process Safety 39

Data adsorption of Calgon-type BPL carbon not to be extrapolated outside these ranges.
Typical criteria apply in gas or vapour adsorption by solid media:

– The greater the molecular weight, the more the adsorption efficiency.
– Non-polar molecules are better adsorbed than soluble molecules.
– Non-soluble molecules are better adsorbed than polar molecules.
– Temperature increase may reduce the degree of adsorption.

1.6 Applications
1.6.1 Kinetics and Equilibrium of Sulphur Oxides

Sulphur dioxide and sulphur trioxide obey the following equilibrium:

SO2 + 0:5O2 >SO3 (1.123)
and (Niessen, 2010):
pSO3
KP ¼ (1.124)
pSO2  pO
0:5
2

5186:5
log 10 KP ¼ + 0:611  log 10 T  6:7497 (1.125)
T
Real distribution of sulphur between dioxide and trioxide depends on many factors, but
conversion to SO3 is accelerated by metals working as catalysts (vanadium). Typically, 2%–4%
appears as trioxide. It has to be considered that conversion to SO3 is promoted by high air
excess, potentially resulting in much greater trioxide percentages.

1.6.2 Properties of Hydrogen Sulphide

See Tables 1.11–1.14.

1.6.3 Properties of Ammonia

See Tables 1.15 and 1.16.

1.6.4 Properties of Sulphur Dioxide

See Tables 1.17 and 1.18.

40 Chapter 1

Table 1.11 Properties of hydrogen sulphide

Name in Air Hydrogen Sulphide
Name in water Sulphydric acid
Formula H2S
CAS number 7783-06-4
EINECS number 231-977-3
UN number 1053
Molecular weight 34.081
TBOIL (Norm) 212.8 K
TCRIT 373.53 K
PCRIT 9 MPa
Gas density Gas density (15°C): 1.422 kg/m3
State at 1 atm 25°C Vapour
Specific gravity 1.17
Flash point 208.4 K (TNO)
AIT (air) 260°C (Glassman and Yetter, 2008)
MIE 0.77 (Glassman and Yetter, 2008)
LEL (1 atm 25°C) 4% (Glassman and Yetter, 2008)
UEL 44% (Glassman and Yetter, 2008)
Hazards Inhalation–Fire–Explosion
Odour Rotten eggs
Odour lower perception threshold 0.00047 (Parthum and Leffel, 1979)
Odour higher perception threshold 100 ppm (Knight and Presnell, 2005)

Table 1.12 Worker exposure limits of hydrogen sulphide

Recommended Limits (ppm)
Limit NIOSH OSHA ACGIH AIHA
IDLH 100 – – –
8-h TWA 10 – 1 –
STEL 15 – 5 –
CEILING 50 10 (10 min) – –
ERPG 1 – – – 0.1
ERPG 2 – – – 30
ERPG 3 – – – 100
 Chemistry of Process Safety 41

Table 1.13 Short-term symptoms and effects of hydrogen sulphide (OSHA, 2016)
Concentration
(ppm) Symptoms/Effects
0.00011– Typical background concentrations
0.00033
0.01–1.5 Odour threshold (when rotten egg smell is first noticeable to some). Odour becomes
more offensive at 3–5 ppm. Above 30 ppm, odour described as sweet or sickeningly
2–5 Prolonged exposure may cause nausea, tearing of the eyes, headaches, or loss of sleep.
Airway problems (bronchial constriction) in some asthma patients
20 Possible fatigue, loss of appetite, headache, irritability, poor memory, dizziness
50–100 Slight conjunctivitis (gas eye) and respiratory tract irritation after 1 h. May cause
digestive upset and loss of appetite
100 Coughing, eye irritation, loss of smell after 2–15 min (olfactory fatigue). Altered
breathing, drowsiness after 15–30 min. Throat irritation after 1 h. Gradual increase in
severity of symptoms over several hours. Death may occur after 48 h
100–150 Loss of smell (olfactory fatigue or paralysis)
200–300 Marked conjunctivitis and respiratory tract irritation after 1h. Pulmonary oedema may
occur from prolonged exposure
500–700 Staggering, collapse in 5min. Serious damage to the eyes in 30min. Death after 30–60
min
700–1000 Rapid unconsciousness, ‘knockdown’ or immediate collapse within 1–2 breaths,
breathing stops, death within minutes
1000–2000 Nearly instant death

Table 1.14 Sectors where hydrogen sulphide may be present.

Sector Levels
Oil and gas Low to very high
Petrochemical Low to very high
Coke production Medium
Sulphur production Medium to high
Industrial wastewater treatment Low to very high
Municipal wastewater treatment Medium
Sewage management Low to high
Waste treatment Low to high
Landfilling Low to high
Slaughterhouses Low to medium
Tanneries Low to medium
Iron smelting Low to medium
Food processing Low to medium
Pulp and paper industry Low to high
Rubber industry Low
42 Chapter 1

Table 1.15 Properties of ammonia

Name Ammonia
Formula NH3
CAS number 7664-41-7
EINECS number 215-647-6
UN number 1005
Molecular weight 17.03
TBOIL (NORM) 239.72 K
TCRIT 405.65 K
PCRIT 11.3 MPa
Gas density Gas density (15°C): 0.711 kg/m3
State at 1 atm 25°C Vapour
Specific gravity 0.58
Flash point  82.4°C (TNO)
AIT (air) 651°C (Glassman and Yetter, 2008)
MIE 14 (Lees)
LEL 15% (Glassman and Yetter, 2008)
UEL 28% (Glassman and Yetter, 2008)
Hazards Inhalation–Fire–Explosion
Odour Pungent
Odour perception threshold 5 ppm (OSHA, 2016)

Table 1.16 Worker exposure limits of ammonia

Recommended Limits (ppm)
Limit NIOSH OSHA ACGIH AIHA
IDLH 300 – – –
8-h TWA 25 25 25 –
STEL 35 35 35 –
ERPG 1 – – – 25
ERPG 2 – – – 150
ERPG 3 – – – 1500

1.6.5 Properties of Sulphur Trioxide

See Tables 1.19 and 1.20.

1.6.6 Properties of Carbon Monoxide

See Tables 1.21 and 1.22.

Another random document with
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 MRS. GASKELL

I
WE think of her habitually—do we not?—by her married title of “Mrs.
Gaskell.” Who Mr. Gaskell was this generation does not, in an
ordinary way, pause to enquire: a neglect which does injustice to a
gentleman of fine presence, noble manners and high culture. She
was a beautiful woman: they married in 1832, and had children, and
lived most happily.
So it is as “Mrs. Gaskell” that we think of her: and I dare to wager
that most of you think of her as Mrs. Gaskell, authoress of Cranford.
Now heaven forbid that anything I say this morning should daunt
your affection for Cranford, as heaven knows how long and sincerely
I have adored it. I have adored it at least long enough and well
enough to understand its devotees—for Cranford has not only
become popular in the sense, more or less, that Omar Khayyam has
become popular—by which I mean that, at this season or
thereabouts, numbers of people buy a copy in limp suède, with Hugh
Thomson’s illustrations, and only hesitate over sending it to the So-
and-So’s with best wishes on a chilling doubt that they sent it last
year, with the identical good wishes—if indeed they are not returning
the identical volume they received! Well, let us be merry and
careless!—in the course of a week or two these soft bricks will be
dropping on every hearth.
But seriously, one finds devotees of Cranford everywhere; and
especially, in my experience, among scholarly old men. They have
Cranford written on their hearts, sometimes hardly covering a
cherished solution of The Mystery of Edwin Drood. Cranford and the
novels of Jane Austen—you never know how many delightful
persons cherish them, have them by heart, pore over their text as
over an Ode of Pindar’s. And they are fierce, these devotees, as the
noble new edition of Jane Austen by Mr. Chapman of the Oxford
Press has recently been teaching us. Here are five volumes edited
with all the care that study and affection can lavish on the task. Yet
from here, there and everywhere lovers start up from firesides—
scattered widowers of this dear maiden—challenging over variae
lectiones, feeling for the hilt on the old hip to champion (we’ll say)
“screen” as the right word against “scene” as printed—

“Swerve to the left, Son Roger,” he said,

“When you catch his eyes through the helmet-slit.”

It is as serious, almost, as all that: and so it is with Cranford, and

Miss Jenkyns and Captain Brown and adorable Miss Matty.
Yet, let us admit there are certain works which conquer some of
us, we cannot tell why. To go a very long way from Cranford, take
Tristram Shandy. No one can really criticise Tristram Shandy, and all
pretence to do so is mere humbug. Either you like Tristram Shandy
(as I do, for one) or you don’t, and there’s an end to it. My sole
complaint against the devotees of Cranford is that, admiring it,
revelling in it, they imagine themselves to have the secret of Mrs.
Gaskell, stop there, and do not go on to explore her other works of
which one at any rate I shall presently dare to proclaim to you as the
most perfect small idyll ever written in English prose.

II
The sin is the worse because every one acknowledges the Life
of Charlotte Brontë to be—after Boswell’s Life of Johnson, admittedly
beyond competition—among the two or three best biographies in our
language. Conceive the Brontës—not Charlotte alone, but the whole
family—the whole of that terrible family in that terrible parsonage at
Haworth—as this staid lady, wife of a Unitarian minister, faithfully
depicts them—the wastrel son, Branwell: through long nights tearing
his own heart out, with his stern old father’s, in the bedroom they
had, for safety, to occupy together: in the end pulling himself up to
die standing: the shuddering sisters listening on the stairs; Emily,
doomed and fierce, she too in her turn standing up to die. Consider
—I will not say Wuthering Heights, or Charlotte’s well-known
magnificent description, in Villette, of Rachel and her tortured acting
—but consider if only by illustration of contrast this most maddened
poem by Emily—and there are others as tragic—
The Prisoner

Still let my tyrants know, I am not doom’d to wear

Year after year in gloom and desolate despair;
A messenger of Hope comes every night to me,
And offers for short life, eternal liberty.

He comes with Western winds, with evening’s wandering airs,

With that clear dusk of heaven that brings the thickest stars:
Winds take a pensive tone, and stars a tender fire,
And visions rise, and change, that kill me with desire.

Desire for nothing known in my maturer years,

When Joy grew made with awe, at counting future tears:
When, if my spirit’s sky was full of flashes warm,
I knew not whence they came, from sun or thunder-storm.

But first, a hush of peace—a soundless calm descends;

The struggle of distress and fierce impatience ends.
Mute music soothes my breast—unutter’d harmony
That I could never dream, till Earth was lost to me.

Then dawns the Invisible; the Unseen its truth reveals;

My outward sense is gone, my inward essence feels;
Its wings are almost free—its home, its harbour found;
Measuring the gulf, it stoops, and dares the final bound.
 O dreadful is the check—intense the agony—
When the ear begins to hear, and the eye begins to see;
When the pulse begins to throb—the brain to think again—
The soul to feel the flesh, and the flesh to feel the chain.

Yet I would lose no sting, would wish no torture less;

The more that anguish racks, the earlier it will bless;
And robed in fires of hell, or bright with heavenly shine,
If it but herald Death, the vision is divine.

Consider, I say, that the authoress of Cranford not only lived with
these fierce women and comforted them as their benign friend, with
a comfort that no soul can give to another without understanding, but
portrayed them (their struggles ended) in a book that combines the
English (even the Victorian English) with the Greek, a fidelity to awful
fact with a serene judgment, a tender mercy—the two so discovering
and covering all, that—whether it be in charity or in justice—its core
of truth has never been challenged: that it stands yet among the
noblest few of English biographies. I put it to you that, if you but set
together those two books—Cranford and the Life of Charlotte Brontë
—at once you must recognise the operating hand—the quietly
operating hand—of genius. But this, even when Mrs. Gaskell’s
longer novels are thrown into the scale, has avoided, I think—
because she herself is so equable, so temperate—its right
recognition. Yes, her very portrait has a Hellenic look, so beautiful it
is, so penetrating its calm gaze.

III
Yet maybe you think it strange that I find so much of high
Hellenic quality in this quiet lady—born a Stevenson, to be sure—but
christened Elizabeth Cleghorn, names not to us reminiscential of
Hybla or the Ilissus. Her father was a Unitarian minister, who
preached in that capacity, in Dob Lane Chapel, Manchester—which
again does not suggest the Acropolis. In 1832 she married a
Unitarian minister, son of a prosperous manufacturer, minister to a
Chapel in Cross Street, Manchester, and prominent on the Home
Missionary Board. For these and some particulars that follow I go to
4
the best sources known to me.

4
Sir Adolphus Ward’s various Introductions to
the Knutsford Edition (8 volumes, published by
John Murray) and the article on her in the
Dictionary of National Biography, by the same
writer, whose scholarship, when devoted to this
dead lady, reaches to a religious note of chivalry.

Her married life was one of unbroken happiness. Her husband

had literary leanings, and in 1838 she writes to Mrs. Howitt, “We
once thought of trying to write sketches among the poor, rather in the
manner of Crabbe (now don’t think this presumptuous), but in a more
beauty-seeing spirit: and one—the only one—was published in
5
Blackwood, January, 1837. But I suppose we spoke our plan near a
dog-rose, for it never went any further.”

5
The curious may read it in Blackwood’s
Magazine, Vol. XLI, No. CCIV, or in Sir Adolphus
Ward’s Biographical Introduction.

So you see that she had already made Manchester her home,
and was already interested in the poor.
Also one may interpose here that (without evidence of her
portrait) she was acknowledged by all who met her to be a person of
quite remarkable beauty, and as little conscious of it as any beautiful
woman has any right to be: since as Jaques noted:
 if ladies be but young and fair,
They have the gift to know it.

Above all, she had the ineffable charm of being the least
assertive, the most concerned with others, in any company. I think
that of her rather than of any other writing-woman one may quote
Mrs. Browning’s lines on her Kate—

I doubt if she said to you much that could act

As a thought or suggestion: she did not attract
In the sense of the brilliant or wise: I infer
’Twas her thinking for others made you think of her.

She never found fault with you, never implied

Your wrong by her right: and yet men at her side
Grew nobler, girls purer, as through the whole town
The children were gladder that pulled at her gown....

The weak and the gentle, the ribald and rude,

She took as she found them, and did them all good:
It always was so with her—see what you have!
She has made the grass greener even here ... with her grave.

Such a woman, as I trace her portrait, was Mrs. Gaskell, and I think
the end of the story will confirm my reading of her. She made no
show: without interfering she saw beauty in the lives of the poor: she
lived with the misery of Manchester and pitied it; and across a
personal bereavement—or (shall we say?) out of the very anguish of
her own breast—she relieved her heart in her first long book in pity
for that place.
In 1844 Mr. and Mrs. Gaskell revisited Festiniog, in North Wales,
a halt of their wedding tour. They took their children with them; and
at the inn there the eldest daughter caught the scarlet fever. Mrs.
Gaskell removed her with her infant brother to Portmadoc, where he
sickened of the fever and died. It was in search of an anodyne for
sorrow that the mother began to write Mary Barton. Read that book
with just these two or three facts in your mind, and you will find an
illustration—though it almost shames me to give you one so poignant
—of the way in which the sincerest art is begotten and brought forth:
that is, by lifting one’s own experience up to a Universal, and then
bringing it back to reclothe it in imaginary, particular, men and
women.

IV
In two previous lectures, Gentlemen, I have given you—it may
well be ad nauseam—the conditions of life among the industrial poor
of that period as they can be gathered from Blue Books and out of
Hansard. In my last lecture I tried to indicate how they affected the
ambitious (and to that extent selfish) but yet chivalrous mind of
Disraeli. I shall be shorter with Mrs. Gaskell, who invents no political
novel, but just tells the tale and passes on. But she tells it, and I
select here to read to you a passage to illustrate rather how gently
and charitably she tells it than to make out the worst of the case,
which yet may be found in her pages.

At all times it is a bewildering thing to the poor weaver to see

his employer removing from house to house, each one grander
than the last, till he ends in building one more magnificent than
all, or withdraws his money from the concern, or sells his mill, to
buy an estate in the country, while all the time the weaver, who
thinks he and his fellows are the real makers of this wealth, is
struggling on for bread for his children, through the vicissitudes
of lowered wages, short hours, fewer hands employed, etc. And
when he knows trade is bad, and could understand (at least
partially) that there are not buyers enough in the market to
purchase the goods already made, and consequently that there
is no demand for more; when he would bear and endure much
without complaining, could he also see that his employers were
bearing their share; he is, I say, bewildered and (to use his own
word) “aggravated” to see that all goes on just as usual with the
mill-owners. Large houses are still occupied, while spinners’ and
weavers’ cottages stand empty, because the families that once
filled them are obliged to live in rooms or cellars. Carriages still
roll along the streets, concerts are still crowded by subscribers,
the shops for expensive luxuries still find daily customers while
the workman loiters away his unemployed time in watching
these things, and thinking of the pale, uncomplaining wife at
home, and the wailing children asking in vain for enough of food,
—of the sinking health, of the dying life, of those near and dear
to him. The contrast is too great. Why should he alone suffer
from bad times?
I know that this is not really the case; and I know what is the
truth in such matters: but what I wish to impress is what the
workman feels and thinks.
But there are earnest men among these people, men who
have endured wrongs without complaining, but without ever
forgetting or forgiving those whom (they believe) have caused all
this woe.
Among these was John Barton. His parents had suffered; his
mother had died from absolute want of the necessaries of life.
He himself was a good, steady workman, and, as such, pretty
certain of steady employment. But he spent all he got with the
confidence (you may also call it improvidence) of one who was
willing, and believed himself able, to supply all his wants by his
own exertions. And when his master suddenly failed, and all
hands in the mill were turned back, one Tuesday morning, with
the news that Mr. Hunter had stopped, Barton had only a few
shillings to rely on; but he had good heart of being employed at
some other mill, and accordingly, before returning home, he
spent some hours in going from factory to factory, asking for
work. But at every mill was some sign of depression of trade!
Some were working short hours, some were turning off hands,
and for weeks Barton was out of work, living on credit. It was
 during this time that his little son, the apple of his eye, the
cynosure of all his strong power of love, fell ill of the scarlet
fever. They dragged him through the crisis, but his life hung on a
gossamer thread. Everything, the doctor said, depended on
good nourishment, on generous living, to keep up the little
fellow’s strength, in the prostration in which the fever had left
him. Mocking words! when the commonest food in the house
would not furnish one little meal. Barton tried credit; but it was
worn out at the little provision shops, which were now suffering
in their turn. He thought it would be no sin to steal, and would
have stolen; but he could not get the opportunity in the few days
the child lingered. Hungry himself, almost to an animal pitch of
ravenousness, but with bodily pain swallowed up in anxiety for
his little sinking lad, he stood at one of the shop windows, where
all edible luxuries are displayed; haunches of venison, Stilton
cheeses, moulds of jelly—all appetising sights to the common
passer by. And out of this shop came Mrs. Hunter, his late
employer’s wife! She crossed to her carriage, followed by the
shopman loaded with purchases for a party. The door was
quickly slammed to, and she drove way; and Barton returned
home with a bitter spirit of wrath in his heart, to see his only boy
a corpse!
You can fancy, now, the hoards of vengeance in his heart
against the employers. For there are never wanting those who,
either in speech or in print, find it their interest to cherish such
feelings in the working classes; who know how and when to
rouse the dangerous power at their command; and who use their
knowledge with unrelenting purpose to either party.

Now you know from actual evidence given you in my two

previous lectures that this account is not overstrained. You see how
the writer makes allowances; and how, all allowances made, her
thrust is as deadly as any in Disraeli’s Sybil.
 V
But now comes in the difference. Mrs. Gaskell knew these
people as Disraeli did not. She had lived among them, and to all the
angry protests evoked by Mary Barton she returned, of her
knowledge, gentle, but gently firm answers which could not be
6
refuted. The story, at any rate, exercised at once a “commanding
effect,” and the width of that effect was attested by translations into
many foreign languages—French, German, Spanish, Hungarian and
Finnish.

6
I should mention here, by the way, on Sir
Adolphus Ward’s authority, the virtual certainty
that before writing her own novel she “had
remained quite unacquainted with both
Coningsby and Sybil.”

She did not go on to exploit that success, that effect. She had
said what she had to say; and having found, in the saying of it, her
gift as a writer, she passed on to other things. A very beautiful
necklace of novels was the result. But this serene indifference to
what might with others have meant a very strong “literary” temptation
implied no failing devotion to the poor whose woes the book had,
once for all, championed. Some eighteen years later, in 1862–3, a
time of trouble came over Manchester and South-west Lancashire in
general, which

called forth one of the most notable, and certainly one of the
best-organized efforts of goodwill and charity which this country
has ever seen. In the long struggle between masters and men,
the times of the Lancashire Cotton Famine, due to the outbreak
and continuance of the American Civil War, brought about a
protracted truce, in which the kindly feelings inspired by the self-
 sacrificing efforts of many leading employers of manufacturing
labour cannot but have counted for much.

I am quoting from Sir Adolphus Ward:

Mrs. Gaskell, whose name had so good a sound among the

Lancashire working classes that we hear of an Oldham man
regularly bringing his children to gaze upon the house in
Plymouth Grove where dwelt the authoress of Mary Barton, gave
many proofs in these times of trouble of her readiness to help
suffering in every way in her power.

The relief problem, in short, claimed her almost entirely during

that long tribulation of her people. “We were really glad,” she writes
to a friend, “to check one another in talking of the one absorbing
topic, which was literally haunting us in our sleep, as well as being
our first thoughts in wakening and the last at night.” In organising,
superintending, working sewing-rooms, providing dinners, she would
work for six or seven hours of her day.
The shadow of these and other industrial troubles recurs,
indeed, in some of the later novels, particularly in North and South:
but always you see that with her there is no political axe to grind, nor
scarce a consciousness of there being any such thing: and this
disinterested charitableness leads her, as it were, imperceptibly into
regions of which Disraeli, with all his genius, never won ken. The first
incentive, I have tried to show, operated on both. But whereas he
went off into a life of action—great and powerful action, let all admit
—to return in his old age to revisit with Endymion the glimpses of the
moon and his boyish dreams, this unambitious Victorian lady, having
found her literary talent, went on to employ it with a serenity
unmoved to worship any idols of the market. Glad of course she was
to enjoy and use her gift: very modestly glad (as what true woman or
man is not?) of the recognition it brought, but following the path to
the end to bequeath to the world several noble novels and three
shining masterpieces. Of these, of course, the Life of Charlotte
Brontë is one and Cranford the second: and for the moment I leave
you to guess at the third. For the moment I wish you to picture this
woman. In her writing, as in her daily life, she had no mannerisms.
She copied neither Disraeli, nor Dickens, who also championed the
poor and was moreover her encourager and editor; nor the Brontës,
for all the spell of their genius; nor Trollope, nor George Eliot; though
all were great and flattered her with their admiration. Past them all
we see her quietly keeping the tenor of her way. Now and again she
seems to falter and ask herself—herself, mind you—Is this trouble to
speak the simple truth as best I can, without heat, really worth its
reward as set against the heat and acrimony it provokes? The
strictures passed on her Life of Charlotte Brontë gave her, for a time,
a distaste for it all. But she wrote on, after a little, and on Sunday,
November 12, 1865, killed of a sudden by a pang of the heart—
carried away, as her epitaph at Knutsford (which is “Cranford”) says,
“Without a moment’s warning”—she left her writings all just as clean
and bright as the bunch of her household keys.

Who sweeps a room, as for Thy laws,

Makes that, and the action, fine.

VI
I shall pass the catalogue of these writings very quickly in review.
The authoress of Mary Barton was hailed at that time, when novels
were yet few and even poetry but beginning to recover its strength,
by great men and by Dickens especially, who engaged her pen for
the first number of his serial adventure, Household Words. In 1853
appeared her second important novel, Ruth (which possibly
influenced Dickens’ own Hard Times, published a year later). Then in
June, 1853, came Cranford, made into a book from papers
contributed to Household Words between December, 1851, and
May, 1853. North and South ran in Household Words from
September, 1854, to January, 1855, and appeared as a book, with
some slight alterations, in that year. In that year also (on March 31st)
Charlotte Brontë died and Mrs. Gaskell consented, at the old father’s
urgent request, to write the Biography. She gave herself up to the
work and finished it in the spring of 1857. The strictures on it—truth,
as Milton says, never comes into the world but as a bastard—broke
her spirit for a while for all but occasional writing: and then came the
cotton famine, of which I have spoken, to tax all her energies. But
after the stress of this they revived. In 1863 appeared Sylvia’s
Lovers, in 1863–4 Cousin Phillis in the pages of the Cornhill
Magazine. In this magazine (August, 1864–January, 1866) followed
her last story, Wives and Daughters, published soon after in that
year as an unfinished work. So you see the whole tale of it lies within
the central years of the last century, beginning with Mary Barton in
1848 and ending sharply just eighteen years after.

VII
I do not propose to discuss the toll of her work this morning. I
wish that those of you who aspire to write, and are here learning to
write, would study it—for two reasons. For the first, while I admit
many flaws, it seems to me elementally of the best literary breeding,
so urbane it is, so disposedly truthful; so much of the world, quizzing
it; so well aware, all the while, of another. For my second, that here
you have, refuting, an exception to all hasty generalisations about
the nineteenth century, the Victorian Age, horsehair sofas, the
Evangelicals, the Prince Consort, the Great Exhibition of 1851 and
all that bagful of cheap rubbish. In 1851 this lady was writing
Cranford: in 1863 she was writing Cousin Phillis: and considering
that most lovely idyll, I am moved to ask, “Do you, at any rate, know
it, this Sicilian yet most English thing of the mid-nineteenth century?”
I am moved to say, “Yes, Keats is lovely, and was lovely to me alas!
before ever you were born: but quit your gushing and your talk about
‘romantic revivals’—which are but figments invented by fellows who
walk round and round a Grecian urn, appraising it scholastically. Quit
it, and try to make a Grecian urn. The horses on the frieze of the
Parthenon are good horses: but you have as good to study to-day or
to-morrow if you will but take a short journey out to Newmarket and
study them. Which is better?—to watch a gallop between two colts
on a heath, or to bend a congested nose over Ferrex and Porrex?”
To be classical is not to copy the classics: to be classical is to
learn the intelligence of the classics and apply just that to this
present world and particularly to this island of ours so familiar and
yet so romantic.

VIII
I spoke, a while back, of three masterpieces of Mrs. Gaskell,
naming two, leaving you to guess the third. Lay by your Cranford,
and take up and study Cousin Phillis.
I suppose its underlying sadness has kept it out of popular
esteem—this tale of scarcely more than a hundred pages—a pale
and shadowy sister of Cranford. It has none, or little of Cranford’s
pawky fun: it has not Cranford’s factitious happy ending. But it beats
me to guess how any true critic can pass it over and neglect a thing
with all that is best in Theocritus moving in rustic English hearts. And
it is not invented. It has in all its movements the suggestion of things
actually seen—of small things that could not have occurred to any
mind save that of an eye-witness—of small recognitions, each in its
turn a little flash of light upon the steady background of rural
England. It is England and yet pure Virgil—as purely Virgilian as the
vignette, in the Fourth Georgic, of the old man of Corycus tilling his
scanty acres:

nec fertilis ilia juvencis

Nec pecori opportuna seges nec commoda Baccho—

who yet brought home his own-grown vegetables at night and cast
them on the table, in his mind equal to the wealth of kings. I shall
read you two passages—the first of young Paul’s introduction, by his
cousin Phillis, to her father the ex-minister and Virgilian scholar
turned farmer and labouring with his hinds—

“There is father!” she exclaimed, pointing out to me a man in

his shirt-sleeves, taller by the head than the other two with whom
he was working. We only saw him through the leaves of the ash-
trees growing in the hedge, and I thought I must be confusing
the figures, or mistaken: that man still looked like a very powerful
labourer, and had none of the precise demureness of
appearance which I had always imagined was the characteristic
of a minister. It was the Reverend Ebenezer Holman, however.
He gave us a nod as we entered the stubble-field; and I think he
would have come to meet us, but that he was in the middle of
giving some directions to his men. I could see that Phillis was
built more after his type than her mother’s. He, like his daughter,
was largely made, and of a fair, ruddy complexion, whereas hers
was brilliant and delicate. His hair had been yellow or sandy, but
now was grizzled. Yet his grey hairs betokened no failure in
strength. I never saw a more powerful man—deep chest, lean
flanks, well-planted head. By this time we were nearly up to him;
and he interrupted himself and stepped forwards, holding out his
hand to me, but addressing Phillis.
“Well, my lass, this is cousin Manning, I suppose. Wait a
minute, young man, and I’ll put on my coat, and give you a
decorous and formal welcome. But—Ned Hall, there ought to be
a water-furrow across this land: it’s a nasty, stiff, clayey, dauby
bit of ground, and thou and I must fall to, come next Monday—I
beg your pardon, cousin Manning—and there’s old Jem’s
cottage wants a bit of thatch; you can do that job to-morrow,
while I am busy.” Then, suddenly changing the tone of his deep
bass voice to an odd suggestion of chapels and preachers, he
added, “Now I will give out the psalm: ‘Come all harmonious
tongues,’ to be sung to ‘Mount Ephraim’ tune.”
He lifted his spade in his hand, and began to beat time with
it; the two labourers seemed to know both words and music,
 though I did not; and so did Phillis: her rich voice followed her
father’s, as he set the tune; and the men came in with more
uncertainty, but still harmoniously. Phillis looked at me once or
twice, with a little surprise at my silence; but I did not know the
words. There we five stood, bareheaded, excepting Phillis, in the
tawny stubble-field, from which all the shocks of corn had not yet
been carried—a dark wood on one side, where the wood-
pigeons were cooing; blue distance, seen through the ash-trees,
on the other. Somehow, I think that, if I had known the words,
and could have sung, my throat would have been choked up by
the feeling of the unaccustomed scene.
The hymn was ended, and the men had drawn off, before I
could stir. I saw the minister beginning to put on his coat, and
looking at me with friendly inspection in his gaze, before I could
rouse myself.

And now let me read you this exquisite passage—there are many
almost as lovely—of Phillis in love, walking with her cousin Paul—
alas! not her beloved.

We talked about the different broods of chickens, and she

showed me the hens that were good mothers, and told me the
characters of all the poultry with the utmost good-faith; and in all
good-faith I listened, for I believe there was a great deal of truth
in all she said. And then we strolled on into the wood beyond the
ash-meadow, and both of us sought for early primroses and the
fresh green crinkled leaves. She was not afraid of being alone
with me after the first day. I never saw her so lovely, or so happy.
I think she hardly knew why she was so happy all the time. I can
see her now, standing under the budding branches of the grey
trees, over which a tinge of green seemed to be deepening day
after day, her sun-bonnet fallen back on her neck, her hands full
of delicate wood-flowers, quite unconscious of my gaze, but
intent on sweet mockery of some bird in neighbouring bush or
tree. She had the art of warbling, and replying to the notes of
different birds, and knew their song, their habits and ways, more
 accurately than any one else I ever knew. She had often done it
at my request the spring before; but this year she really gurgled,
and whistled, and warbled, just as they did, out of the very
fulness and joy of her heart. She was more than ever the very
apple of her father’s eye; her mother gave her both her own
share of love and that of the dead child who had died in infancy.
I have heard cousin Holman murmur, after a long dreamy look at
Phillis, and tell herself how like she was growing to Johnnie, and
soothe herself with plaintive inarticulate sounds, and many
gentle shakes of the head, for the aching sense of loss she
would never get over in this world.

My eyes, to be sure, are not what they were: but to them the
prose of this shimmers with beauty. In Mrs. Gaskell, as with many
another ageing writer, one can detect towards the close a certain
sunset softness—a haze, we may call it—in which many hard
experiences are reconciled. To take the highest, we agree that it so
happened to Shakespeare. To step down to the man with whom for a
study in the differences of literary genius starting from a like
incentive—the woes of the poor, and operating in the same literary
form, the novel—I have been—I hope, Gentlemen, not whimsically—
contrasting this very noble lady, we know that in his later days, in
Endymion, Disraeli saw his youth so, casting back to it. And you,
maybe, will say that these sunset softening colours are all a mirage.
Well, a great deal of it all is that. I believe that, as you grow older,
you will find yourselves more and more tending to make less, and
still less, account of definitions, of sharp outlines and judgments
based on them; of anybody’s positive assertions, be he never so
young.

IX
I have been speaking, however, to-day of one whose measure in
any light has never to my thinking been accurately taken. The crew
of Odysseus were Greeks. They beached their ship (says Homer) on
the isle of the Laestrygonians: and there came down to them the
Queen of the Laestrygonians, “a woman as tall as a mountain,” and
they hated her. The Victorian Age lent itself to excess; and its
excessive figures are our statues for some to deface or bedaub. But
I, who have purposely compared Elizabeth Gaskell with her most
ornate contemporary, dare to prophesy that when criticism has sifted
all out, she will come to her own, as a woman of genius, sweetly
proportioned as a statue, yet breathing; one of these writers we call
by that vain word—so vain, so pathetic even when used of the
greatest poet—“immortal.”
 ANTHONY TROLLOPE
THE BARSETSHIRE NOVELS

I
A few months ago I asked a publisher if he had ever thought of
venturing on a complete edition of Trollope, and was answered that
he had thought of it often, but doubted it would not pay. A few weeks
ago I referred this answer to an eminent bookseller, and he praised
the publisher’s judgment. I retain my belief that the pair of them are
mistaken: for let the name of Trollope be mentioned in any company
of novel-lovers, almost to a certainty one or two will kindle, avow a
passion for him, and start a chorus of lament that there exists no
complete worthy edition of him.
“All Balzac’s novels occupy one shelf”—and all Trollope’s would
occupy a plaguey long one. Some of them, too, are hasty, baddish
novels. None the less, I see that shelf as one of trusted and familiar
resort for such a number of my fellows as would fill a respectable
subscription-list: and, anyhow, it remains a scandal that certain good
works of his—The Eustace Diamonds, for instance—are
unprocurable save by advertising for second-hand copies. Mr.
Humphrey Milford, of the Oxford University Press, has recently
printed The Claverings and The Belton Estate in the World’s
Classics, with the Autobiography, which did, as it happened, about
as much harm as a perfectly honest book could do to an honest
man’s fame. Messrs. Chatto & Windus—whom, as Cicero would say,
“I name for the sake of honour,” as publishers who respect their
moral contract to keep an author’s books alive while they can—have
kept on sale some eight or nine, including The American Senator,
The Way We Live Now, and The Golden Lion of Grandpré; and the
famous Barsetshire six, of which Messrs. George Bell now offer us a
 7
cheap and pleasant reprint, have always been (as they say in
Barset) “come-at-able” in some form or another. But while three full
editions of Stevenson have been subscribed for since his death in
1894 (the first of them fetching far more than the original price), and
his sale in cheaper editions has been high and constant, Trollope,
who died in 1882, has, in these forty-odd years, received no
gratitude of public recognition at all answerable to his deserts.

7
Trollope’s Barsetshire Novels: (1) The
Warden, (2) Barchester Towers, (3) Dr. Thorne,
(4) Framley Parsonage, (5) The Small House at
Allington (2 vols.), (6) The Last Chronicle of
Barset (2 vols.) 8 vols. 25s. the set. (Bell &
Sons.)

It is a curious business in two ways. For the first, the rebirth of

Trollope’s fame, with the growing readiness of an admirer to cast
away apology and hail a fellow-admirer as a friend “by adoption
tried,” has nothing esoteric about it. A passion for Peacock, or for
Landor—as a passion for Pindar—you may share with a friend as a
half-masonic, half-amorous secret. But there can be no such
freemasonry over Trollope, who is as English as a cut off the joint or
a volume of Punch. For the second curiosity, I suppose that no man
ever wrote himself down at a more delicately ill-chosen time than did
Trollope by the publication (posthumous) of his Autobiography in
1883. It was a brave—if unconsciously brave—and candid book. But
it fell on a generation of young men fired in literature by Flaubert, in
painting (say) by Whistler; on a generation just beginning to be
flamboyant over “art for art’s sake,” the mot juste, and the rest. It all
seems vain enough at this distance, and the bigots of each
successive iron time will always be arraigning their fathers’ harmless
art, no doubt to the ultimate advancement of letters. But by young
men quite honestly and frenetically devoted to chiselling out English
as though (God rest them!) in obedience to a Higher Power, it may