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HYDROMETALLURGY
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HYDROMETALLURGY
Practice
Volume 2
MICHAEL NICOL
Murdoch University, Murdoch, WA, Australia
with contributions by
NICHOLAS WELHAM
GAMINI SENANAYAKE
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
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Copyright Ó 2022 Elsevier Inc. All rights reserved.
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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.
ISBN: 978-0-323-99214-5
For information on all Elsevier publications visit our website

at https://www.elsevier.com/books-and-journals
Publisher: Candice Janco

Acquisitions Editor: Anita Koch
Editorial Project Manager: Mica Ella Ortega
Production Project Manager: Paul Prasad Chandramohan
Cover Designer: Miles Hitchen
Typeset by TNQ Technologies

Contents
1 Leaching practice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Leaching methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Typical leaching processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Batch leaching kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4 Continuous leachingdmicro- and macrofluids . . . . . . . . . . . . . . . . . . 6
1.5 Counter-current leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.6 Bacterial oxidation and leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.7 Pressure leaching. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.8 Heap leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.9 In situ leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
1.10 Leaching of gold and silver. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.11 Alternative lixiviants for gold . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
1.12 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
Problemsdleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Case study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Appendix. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
Further reading. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2 Solideliquid separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
2.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
2.2 Sedimentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
2.3 Thickeners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
2.4 Filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
2.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
Further reading. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
Case study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
vi Contents
3 Precipitation and crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85

3.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.2 Thermodynamics of precipitation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.3 Iron removal from zinc sulfate solutions. . . . . . . . . . . . . . . . . . . . . . . . . 99
3.4 Kinetics of precipitation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
3.5 Dissolutioneprecipitation processes. . . . . . . . . . . . . . . . . . . . . . . . . . . 109
3.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
Case study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
4 Solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117

4.1 A typical SX process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
4.2 Chemistry of SX processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
4.3 Extraction methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
4.4 Common SX contactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
4.5 Some SX processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
4.6 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Case study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
Further reading. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
5 Adsorption and ion exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171

5.1 Ion-exchange resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
5.2 Speciality resins and adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
5.3 Ion-exchange equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
5.4 Ion-exchange kinetics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
5.5 Ion-exchange processes and equipment. . . . . . . . . . . . . . . . . . . . . . . 190
5.6 Process examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
5.7 Quantitative description of fixed-bed processes . . . . . . . . . . . . . . . 196
5.8 Mass transport parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
Contents vii
5.9 Modeling of breakthrough. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203

5.10 The resin (carbon)-in-pulp process . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
5.11 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
Case study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
Appendix 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
Appendix 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
Appendix 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Appendix 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Literature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
6 Cementation and reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247

6.1 Cementation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
6.2 Reduction by dissolved gas. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
6.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
Reference . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
7 Electrowinning and electrorefining of metals. . . . . . . . . . . . . . . . . . . . . . 271

7.1 General considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271
7.2 Mass transfer at vertical electrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . 277
7.3 Electrocrystallization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
7.4 Current distribution in cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
7.5 Materials for cells and electrodes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
7.6 Tankhouse current distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
7.7 Energy consumption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
7.8 Electrorefining of metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 314
7.9 Electrowinning of copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
7.10 Electrowinning of zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328
7.11 Electrowinning of nickel and cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . 340
7.12 Electrowinning of manganese metal and dioxide . . . . . . . . . . . . 350
viii Contents
7.13 Electrowinning in novel cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362

7.14 Economic optimization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
7.15 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
Case study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
Further reading. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
8 Process selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395

8.1 Process selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
Further reading. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
Leaching practice
1
The chemistry of processes aimed at the dissolution of
valuable metals from various feed materials was covered in
Chapter 6 in Volume 1. In this chapter, the various methods
employed to carry out the leaching reactions will be outlined
The choice of a particular leach process and the equipment to
be used depends on the performance that can be achieved by the
various options. The main factors to be taken into account in
assessing leach performance are the following.
• Degree of dissolution of desired species.
• Selectivity of leaching process with respect to the desired
species.
• Leaching time required to achieve the desired extraction.
• Operating cost (lixiviants, power).
• Capital cost.
There is generally an economic optimum that determines the
most appropriate strategy for leaching. Thus, for the leaching of
gold ores, the objective should be to maximize extraction given
that operating costs are generally not high relative to the value
of the product. On the other hand, in the case of the leaching
of low-grade copper ores, the operating costs are the most impor-
tant consideration and heap leaching is the only viable option.
Even in this case, high acid consumption can rule out heap leach-
ing for some ores.
1.1 Leaching methods

The techniques shown next are applied in the leaching of ores
and concentrates.
In situ leaching: Lixiviant pumped directly into fractured ore-
body and pregnant solution recovered.
Hydrometallurgy. https://doi.org/10.1016/B978-0-323-99214-5.00006-1
Copyright © 2022 Elsevier Inc. All rights reserved. 1
2 Chapter 1 Leaching practice
Heap (or dump) leaching: Lixiviant sprinkled over heaps of

mined (crushed) ore in heaps built over the impervious base.
Vat leaching: Crushed ore fills a large vat that is then filled with
lixiviant and left to leach. A batch process that is not very
common.
Chapter 1 Leaching practice 3
Agitation leaching: Milled ore contacted with lixiviant in

agitated tanks (mechanical or air sparging). Batch or multistage
continuous reactors.
Pressure leaching: Milled ore or concentrate contacted with lixi-

viant in high-pressure, high-temperature reactors (autoclaves)
that are generally operated in continuous mode.
Bacterial leaching: A variation of heap or agitation leaching in

which bacteria assist in the leaching reactions.
Some of the more important practical methods used to
dissolve or leach valuable components of an ore, concentrate,
or other intermediate product are summarized in Fig. 1.1. The
actual method to be adopted depends largely on the value of
the material to be treated with low-grade materials requiring
methods to the left and high grade materials to the right of the
diagram.
1.2 Typical leaching processes

The dissolution of a solid species is a chemical reaction that
can be classified into one of several types such as acid leaching
Ore
Lix. Lix.
In-Situ Heaps Crush Crush Crush

Lix.
Vat Grind Grind

Lix.
Tank Treat
Lix.
Tank
Months to Years Days Mins to hours
Increasing value of material leached
Figure 1.1 Selection of leaching method with grade of feed material.
and oxidative leaching as outlined in Chapter 6 in Volume 1. The

chemistry that is possible in the dissolution of a solid is often exten-
sive and varied and depends on the ingenuity of the researcher.
However, practical considerations determined largely by the cost
of the lixiviant have restricted the choice of the leaching process.
Table 1.1 summarizes some of the more important leaching
processes that are in operation in various parts of the world.
The design and operation of leaching processes are critically
dependent on an understanding and application of the kinetics
of the reactions taking place in leach reactors. In the following
sections, we will show how kinetic information can be used to
describe how we can design and operate a leaching process.
1.3 Batch leaching kinetics

In Chapter 6 in Volume 1, we dealt with the expected profiles
for the leaching of particles for several cases in which the
Table 1.1 Some leaching processes in operation.
Feed Lixiviant Oxidant Temp. Pressure Equipment

Oxidized Cu ore Dil H2SO4 None Ambient Atmos. Heaps
Sulfide Cu ore Dil H2SO4 Ferric, bacteria Ambient Atmos. Heaps
Cu, Ni, Co, Zn Dil H2SO4 Ferric, oxygen >100 C 1e10 bar. Tanks,
concentrates, autoclaves
mattes
Zinc calcine Dil H2SO4 None 40e90 C Atmos. Tanks
Ni matte Dil HCl Ferric, cupric <100 C Atmos. Tanks
Ni laterite ore Dil H2SO4 None 250 C 50 bar. Autoclaves
Reduced laterite ore NH3/CO2 Air, Cu(II) 40e80 C Atmos. Tanks
Uranium ore Dil H2SO4 Ferric þ MnO2 40e50 C Atmos. Tanks, in situ
Oxidized gold ore NaCN Air Ambient Atmos. Heaps, tanks
Refractory Au ore, H2SO4/NaCN Ferric/Air 150e200 C/Ambient 30e40bar/Atmos Autoclaves/
concentrates tanks
Bauxite NaOH None 150e200 C 20e40 bar Autoclaves
Roasted V ore Water None 50e90 C Atmos. Tanks, columns
Scheelite Soda ash None 200 C 40 bar Autoclaves
Roasted Li ores Dil H2SO4 None <100 C Atmos. Tanks
rate-determining step is either mass transport or chemical reac-

tion. In many real cases (see later) involving ores and, to a lesser
extent, concentrates, the curve of fraction leached versus time
does not conform to any of the theoretical forms. Under these
conditions, we have to resort to empirical rate equations.
Consider the leaching of a typical gold ore for which the
following rate equation has often been found to describe the
rate of dissolution of gold from cyanide pulp,
2
d½Au=dt ¼ k ½Au ½Auf (1.1)
in which [Au] is the concentration (mass gold/unit mass of pulp)

at any time, t, and [Au]f is the corresponding concentration after
an infinite time, that is, it is the ultimate achievable barren con-
centration (mainly “locked gold” not accessible to the lixiviant).
k is a rate constant.
This equation can be integrated to give,

1= ½Au ½Auf 1= ½Auo ½Auf ¼ kt (1.2)
where [Au]o is the initial concentration. This equation can be writ-

ten in the form
X ¼ K0 t=ð1 þ K0 tÞ (1.3)
in which k0 ¼ k([Au]o[Au]f) and X ¼ ([Au][Au]f)/([Au]o[Au]f) is

the fraction of gold leached.
The parameters [Au]f and k can be obtained from a small-scale
batch leach carried out under typical envisaged plant conditions
of pulp density, cyanide concentration, and pH. For example,
the time required to achieve a 50% dissolution of gold from a
batch of pulp for which [Au]o ¼ 5 g/t, [Au]f ¼ 0.2 g/t, and
k ¼ 0.05/h, will be given by
t ¼ fð1 = 2.3 1 = 4.8Þg=0.05 ¼ 4.5h
In a practical situation, the time required to fill and empty the
batch reactor will have to be added to the actual leaching time.
This generally is most efficient with large reactors.
Thus, for a batch leach plant to treat 100 t/h of the above pulp
in a tank that can hold 950 t (for comparison with a later sectiond
see Appendix) of pulp, the leach time will be 4.5 h, which will leave
4.5 h for charging and discharging the tank, that is, an average
pulp flow-rate of 420 t/h during these operations.
Notice that in the case of a batch reactor, all of the ore parti-
cles are exposed to the lixiviant for the same leaching period.
Batch leaching is seldom used in practice except for relatively
small-scale operations such as, for example, the dissolution of a
precious metal concentrate (gold and/or platinum group metals)
in, for example, a chlorine/chloride system. The requirement for
accurate accounting of the metal in various stages of processing
is also considerably simplified in batch processing. The formation
of metastable species in solution (such as hydrated silica) may
also be controlled more appropriately in a batch rather than in
a continuous reactor.
1.4 Continuous leachingdmicro- and

macrofluids
In continuous leaching, the ore, concentrate, or other material
containing the metal or mineral to be leached (generally as a
slurry) and the lixiviant are fed continuously into a stirred tank
reactor (CSTR) and the leached slurry discharged continuously
generally into another reactor in series.
The analysis of the performance of this type of reactor de-

pends on the nature of the fluid. Microfluids consist of solutions
such that one cannot distinguish one molecule of a solute, such as
an ion or solvent molecule from another. Thus, in a CSTR treating
a microfluid, all reactants are at their exit (i.e., low) concentra-
tions, reactants entering are immediately diluted to exit concen-
trations by perfect mixing, and the reactions, therefore,
take place at a relatively low rate, as dictated by the reactant con-
centrations. The flow of a microfluid is often characterized as
nonsegregated.
On the other hand, as shown in Fig. 1.2, macrofluids consist of
suspensions of particles each of which is distinguishable and each
of which is an aggregate (crystal in some cases) of a large number
of atoms or molecules. Thus, for example, a particle of ore sus-
pended in a slurry will behave in a CSTR in the same way as a
batch reactor. Thus, the reactant concentrations (in the solid
phase) do not immediately drop to a low value but decrease as
they would in a batch reactor and the extent of reaction in each
of the ore particles in the reactor depends only on the length of
stay (residence time) in the reactor. This is equally true for any
particle in the exit stream. Thus, the fractional conversion in the
exit stream is determined by summing the conversions of all the
particles (Population Balance Method). This is an example of
segregated flow.
Thus, in a CSTR treating a slurry, the solution phase would
behave as a microfluid and the solid phase as a macrofluid.
Thus, in an ideal CSTR in which all particles of the above gold
ore have the same residence time tR (¼ Vol. of reactor/Volumetric
flowrate of slurry), the performance would be identical to that of
the batch reactor discussed earlier.
Figure 1.2 Schematic to distinguish between microfluid (left) and macrofluid (right).
1.4.1 Residence time distribution in a CSTR

In an ideal completely mixed reactor vessel, an entering fluid
element is instantaneously broken up into tiny fragments that are
uniformly distributed throughout the volume of the vessel. Some
of these fluid fragments are immediately drawn into the effluent
stream while others circulate within the vessel for various lengths
of time before finding their way out. Thus, at any instant, the
reactor effluent is composed of fluid particles that have spent
various lengths of time in the vessel. In contrast, every fluid
element entering a plug flow vessel follows the element that
entered before it without any intermixing and exits the reactor
in exactly the same order. At any instant then, the exit stream is
made up of fluid elements, all of which have been resident in
the reactor for exactly the same length of time. The time spent
in the reactor by a fluid element is called its exit age. The distribu-
tion of exit ages of all fluid fragments in the reactor effluent is
called the residence time distribution (RTD) and is indicative of
the mixing and flow distribution patterns within the reactor.
In theory, in a “perfectly mixed tank”, the residence times
cover the whole range from zero to infinity, although the average
or mean residence time (tR) is the same as for batch treatment,
namely the mass of pulp in the tank divided by the mass flowrate.
Mixing theory shows that the way to overcome the “short-
circuiting” that occurs in a single tank is to divide the same total
volume or mass among a number of tanks in seriesdthe more
tanks there are in series, the higher will be the proportion of
pulp that will have a residence time close to the mean value.
For the mean residence time, tR ¼ V/Q, in which V is the vol-
ume of fluid in the tank and Q the volumetric flowrate, the actual
residence time/mean residence time ¼ t/tR ¼ q.
The residence time distribution function, E(q), is the relative
proportion of the discharge pulp having a residence time be-
tween q and q þ dq. That is, E(q).dq is the fraction of the exit
stream of age between q and qþdq.
For an ideal plug flow reactor, the expected RTD function, E(q)
is shown as the vertical arrow in Fig. 1.3.
On the other hand, for a completely mixed (CSTR) reactor,
1
EðqÞ ¼ expðqÞ (1.4)
tR
A graphical representation of the expected RTD function for a
completely mixed vessel is shown in Fig. 1.3.
Consider a number of i mixed tanks in series that are assumed
to be completely mixed and to each have the same volume. Thus,
0.8
0.6
θ)
E(θ
0.4
0.2
0
0 1 2 3
θ
Figure 1.3 Residence time distribution for a single CSTR.
if the total vessel volume is V, each tank has volume Vi ¼ (V/N).

The RTD function for this situation can be derived and is given by
NN
$eðNqÞ
N1
EðqÞ [ ½q (1.5)
ðN 1Þ!
A family of RTD curves for a number of tanks in series is
shown in Fig. 1.4.
The fraction of fluid that has a residence time between q1
and q2 is given by that area under the curve between q1 and q2
relative to the total area under the curve. These values are shown
in Table 1.2 for several intervals.
Figure 1.4 Residence time distributions for tanks in series.

Table 1.2 Fraction of fluid with various residence times.
Reactors, N 1 2 3 5 10
Mean t/s Range t/s Fraction Fraction Fraction Fraction Fraction
0.1 0e0.2 0.1814 0.0596 0.0248 0.0046 0.0001
0.3 0.2e0.4 0.1485 0.1286 0.0967 0.0499 0.0094
0.5 0.4e0.6 0.1216 0.1457 0.1480 0.1314 0.0773
0.7 0.6e0.8 0.0996 0.1375 0.1604 0.1853 0.1979
0.9 0.8e1.0 0.0815 0.1189 0.1463 0.1876 0.2563
1.1 1.0e1.2 0.0667 0.0976 0.1204 0.1552 0.2148
1.3 1.2e1.4 0.0546 0.0774 0.0926 0.1122 0.1334
1.5 1.4e1.6 0.0447 0.0599 0.0678 0.0736 0.0667
1.7 1.6e1.8 0.0366 0.0456 0.0479 0.0449 0.0283
1.9 1.8e2.0 0.0300 0.0342 0.0329 0.0259 0.0106
2.1 2.0e2.2 0.0246 0.0253 0.0221 0.0142 0.0036
2.3 2.2e2.4 0.0201 0.0186 0.0145 0.0076 0.0011
2.5 2.4e2.6 0.0165 0.0136 0.0094 0.0039 0.0003
2.7 2.6e2.8 0.0135 0.0098 0.0060 0.0020 0.0001
2.9 2.8e3.0 0.0110 0.0054 0.0012 0.0003 0.0000
>3.0 0.0490 0.0224 0.0089 0.0015 0.0000
It is apparent that as the number of tanks increases, the distri-

bution of residence times becomes sharper with a larger fraction
of the pulp having a residence time close to tR.
For a reaction in the tank that is a first-order process, it can
be shown that no error is introduced by assuming that all parti-
cles have the same (mean) residence time. This is not true for any
other reaction order (see Appendix for details).
The situation with reactions involving solid particles is further
complicated by the fact that a pulp invariably contains solids with
a nonuniform particle size distribution, probable different
shapes, and even a distribution of reactivities. Thus, Fig. 1.5
shows a mineral liberation analyzer picture of the gold particles
(blue) in a typical gold concentrate produced by gravity
separation.
Thus, one could expect to find a distribution of residence
times, particle sizes, shapes, and reactivity such as shown in
Fig. 1.6.
It is not difficult to visualize that the larger particles will prob-
ably have a longer residence time in the tank and may, if large
Figure 1.5 Distribution of particle sizes and shapes in a gold (blue (dark gray in print)) concentrate. The green
particles (light gray in print) are pyrite.
Fraction
Within
Each
Class
Particle size, shape, reactivity

Figure 1.6 Schematic distribution of various characteristics of ore/concentrate particles.
enough, settle in the bottom of the tank while the fine particles
will probably have a shorter mean residence time. This effect
will, in part, act to compensate for the normal RTD in that we
want the larger particles to have a longer residence time. For
this reason, the complications caused by the RTD effect are often
ignored.
In a real agitated tank reactor, however, there is often a degree
of short-circuiting of the pulp due to inefficient blending of the
incoming pulp with the contents of the tank coupled to inappro-
priate positioning of the feed and exit points. The settling of
larger particles can also often result in a significant fraction of
the tank volume being unavailable for reaction. This is, as ex-
pected, more prevalent in the first tank in a series and the peri-
odic use of tracer tests to establish the active volume of the
tank will enable this problem to be highlighted.
It is apparent that a full treatment of the kinetics of leaching
of a real ore or concentrate will require information on the parti-
cle size distribution. Given all the previously mentioned compli-
cations when dealing with real leach systems, the added
complexity of the population balance models cannot generally
be justified. The Appendix outlines the application of conven-
tional CSTR theory for the treatment of leaching reactions
bearing in mind the previously mentioned problems in particu-
late systems.
1.5 Counter-current leaching

The previously mentioned leaching processes involve cocur-
rent flow of the ore or concentrate and the lixiviant. While this
is often a convenient method of operating, greater efficiencies
in terms of overall leaching recovery and maximum utilization
of the lixiviant can be accomplished by contacting the lixiviant
with the ore in a counter-current fashion. Thus,
• Maximum extraction is achieved by contacting a leach residue
with fresh, concentrated lixiviant.
• Maximum utilization of the lixiviant can be achieved by con-
tacting fresh, reactive ore or concentrate with lixiviant that
has already been used in a prior stage.
Thus, consider the real example shown in Fig. 1.7 of a three-
stage leaching circuit for a zinc calcine that is designed to
maximize zinc recovery and utilize all the lixiviant while still mini-
mizing the dissolution of iron by limiting the pH to values above 3
in the first stage leach and providing a solution of the desired
composition for purification before electrowinning.
As this is the first example of a typical hydrometallurgical flow-
sheet, it is worth spending some time on the details. Ignore in the
first instance the operations shown in dashed linesdthese are
used to bleed iron from the circuit and are not essential in terms
of counter-current leaching and we shall return to this section
later. In terms of overall leaching in one stage, one is simply
reacting the calcine with acid in the spent electrolyte from elec-
trowinning that contains excess acid generated at the anode dur-
ing electrowinning. However, in this case, in the first leach stage,
the calcine is contacted with (a) solution from the second stage
leach that contains excess acid and zinc dissolved in the first
Calcine
1st Stage Leach, 50oC, pH 4
Spent L
Electrolyte SLL
2nd Stage Leach, 80oC, 10 g/L acid Calcine, NH 4+
L
SLLL
L
3rd Stage Leach, 80oC, 50 g/L acid SLL
S
LLL Residues
Figure 1.7 A three-stage counter-current leaching process for zinc calcine.
stage and (b) small amounts of spent electrolyte to control the pH

of the solution leaving the first stage. The pulp leaving the first
stage is filtered (or settled) to separate the solution from the
leach residue. The solution now contains up to 200 g/L zinc
and is sent to the purification stage of the plant and thereafter
to electrowinning.
The solid residue from the first stage still contains zinc and is
subjected to leaching under more extreme conditions to dissolve
most of the residual zinc. The solution used to dissolve this zinc is
made up of a solution from the third stage leach and some spent
electrolyte. The pulp from this stage is subjected to solid/liquid
separation and the solution is routed to the first stage and a small
amount is sent for iron removal. The solid from this second stage
is the feed to the third stage in which any residual refractory zinc
is dissolved at high temperature and acidity using the spent elec-
trolyte. After solid/liquid separation, the solution phase is used in
the second stage leach, and the solid is washed and reported as
the final residue.
While this approach is efficient in terms of leaching, the intro-
duction of a solid/liquid step between each counter-current stage
introduces an additional unit operation that can be both ineffi-
cient and costly for pulps that are difficult to filter or settle. The
introduction of additional water for washing the filter cakes

further complicates the process. For this reason, counter-
current leaching is not applied as widely as may be anticipated.
1.6 Bacterial oxidation and leaching

Bioleaching is the extraction of a metal from sulfide ores or
concentrates using microorganisms that catalyze the oxidation
of sulfide minerals. An associated process is biooxidation in which
sulfide minerals associated with but not necessarily part of the
mineral of interest is oxidized or dissolved. In biooxidation of re-
fractory gold ores, bacteria are used to solubilize an iron sulfide in
which the gold particles are located and thus make the gold avail-
able for cyanide leaching. Likewise, in coal desulfurization, bacte-
ria are used to oxidize the pyrite contaminant in the coal thus
making the sulfur soluble as ferric sulfate.
Bioleaching is used today in commercial operations to process
ores of copper, nickel, cobalt, zinc, and uranium; whereas, bio-
oxidation is used in gold processing and coal desulfurization.
Since bioleaching is a natural process, an undesirable effect is
the creation of so-called acid drainage from the slow oxidation
of sulfide mineral outcrops and from abandoned tailings dumps.
Bioleach processing differs depending on the type of resource
to be processed.
Dump leachingdwaste rock, low-grade ore, or concentrator
tailings (low grade, oxides, and secondary sulfides) are leached
from waste dumps.
Heap leachingdnewly mined run-of-the-mine (ROM) material
(intermediate grade, oxides, and secondary sulfides) is placed as a
heap on an impervious natural surface or a pad and leached. ROM
may be leached as mined or may be partially crushed and mixed
with acid before depositing on the heap.
Agitated leachingdconcentrates are leached in a tank using
mechanical agitation.
Waste dump leaching uses mesophilic (ambient temperature,
35e45 C) microorganisms, that is, bacteria. Heap leaching of
ore may involve mesophiles or moderate thermophiles (high tem-
perature, 50e60 C) microorganisms. Leaching of chalcopyrite
and other primary sulfide concentrates requires extreme thermo-
philes (>70 C). A photograph of thiobacillus ferrooxidans bacteria
attached to sulfide minerals is shown in Fig. 1.8.
In summary, bioleaching involves
• Oxidative dissolution of sulfides with ferric ions.
• Reoxidation of ferrous by dissolved oxygen catalyzed by spe-
cific bacteria.
Figure 1.8 Bacteria (yellow (light gray in print)) associated with sulfide minerals.
• Use of microorganisms of which thiobacillus ferrooxidans and

sulphooxidans are most common.
• Source of CO2, pH about 1.5e2, temperature 35e45 C, nutri-
ents (N, P, K), dissolved O2 greater than 1 ppm.
For example, the following reactions occur during the bio-
oxidation of pyrite,
FeS2 ðsÞ þ 14Fe3þ D 8H2 O ¼ 15Fe2þ D 2H2 SO4 D 12Hþ (1.6)
14Fe2 D þ 7=2O2 þ 14Hþ ¼ 14Fe3þ D 7H2 O (1.7)
that is, overall,

2FeS2 ðsÞ þ 15=2O2 D H2 O ¼ Fe2 ðSO4 Þ3 þ H2 SO4 (1.8)
N.B. In the case of pyrite, acid is produced and must be
neutralised.
In the case of pyrrotite,
2FeSðsÞ þ 9=2O2 þ H2 SO4 ¼ Fe2 ðSO4 Þ3 þ H2 O (1.9)
acid is consumed and must be provided to keep the pH in the op-

timum region.
Some of the most important advantages of biooxidation or
leaching processes are
• Rapid oxidation of iron(II) to iron(III)
• Bacterial oxidation of elemental sulfur layers
• Lower capital costs for small to medium size plants
• Relatively simple, low-tech process
• Environmentally acceptable
On the other hand, there are some disadvantages such as

• Slow kinetics (several days under favorable conditions)
• Sensitivity to process variations (temperature, loss of aeration,
poisons such as cyanide and salinity)
• Limited solids content (<20%)
• Produces soluble iron(III) that requires removal and disposal.
• Bioleaching does not recover the precious metals in the ore
1.6.1 Process parameters for biological oxidation

The plant size is determined by the ore or concentrate
throughput and the rate of oxidation of sulfide sulfur. The relative
proportions of each mineral present determine the process acid
consumption/production, oxygen demand, and cooling require-
ments as shown in Table 1.3.
Major design requirements of reactors are:
• Agitation to suspend solids and, more importantly, to disperse
large volumes of air or oxygen.
• Cooling coils to dissipate heat generated by exothermic reac-
tions and agitation that is not lost by evaporation, heating of
air, and feed pulp.
Table 1.3 Reagent and power requirements.
Oxygen
S, Heat of Reaction demand H2SO4
Mineral % kJ/kg kJ (kg/S) kg (kg/S) Demand kg /kg
Pyrrhotite 36.4 11,373 31,245 2.25 0.558
FeS
Arsenopyrite 19.6 9415 48,036 3.51 0.301
FeAsS
Pyrite 53.3 12,884 24,173 1.88 0.408
FeS2
Chalcopyrite 34.9 9593 27,505 2.13
CuFeS2
Chalcocite 20.1 6201 30,811 2.50
Cu2S
Pentlandite 33.2 10,174 30,644 2.20
(Ni,Fe)9S8
Dolomite 0 219 e e 0.979
Ca(Mg) (CO3)2
• Residence time
• Corrosion resistance of the materials of construction given
acidic conditions.
1.6.2 Biooxidation reactor kinetics and design

The rate of biological oxidation of a sulfide mineral can often
be expressed in terms of the “logistic rate equation”
v ¼ dX=dt ¼ k$X½1 X = X m (1.10)
where v is the rate of oxidation,

X is fraction oxidized,
Xm is the max. fraction that can be oxidized, and
k is a bacterial growth rate constant
Consider a single-stage CSTR reactor containing a volume V of
pulp that is flowing at a rate Q (volume/unit time) through the
reactor.
From the mass balance at steady-state, we obtain the CSTR
equation,
X ¼ V=Q$dX=dt (1.11)
and, substituting the previous rate equation,

X ¼ X m ð1 Q = kVÞ ¼ X m ð1 1 = ktR Þ (1.12)
in which tR ¼ V/Q is the mean residence time.
For k ¼ 1/tR, X ¼ 0, and this is referred to as the bacterial cell
“wash-out” condition that is, the operating point at which the
dilution rate, 1/tR, is equal to the maximum rate of growth of
the bacterial cells. Thus,
(a) For three equal reactors in series:
Cell wash-out will occur for tR ¼ 1/k and the system residence
time will be 3tR
(b) For a primary reactor that is twice the size of the secondary
reactors cell wash-out will occur for a total residence
time ¼ 2/k ¼ 2tR where tR is the residence time in the primary
reactor.
This is the basis for the common design of two primary reac-
tors in parallel feeding secondary reactors of the same size in se-
ries. This ensures that wash-out of the bacteria will not occur at
the design flow rates for a single reactor.
Fig. 1.9 illustrates this phenomenon for a bioleach reactor in
which a refractory gold concentrate is oxidized. The gold recovery
shown is that obtained by cyanidation of the residue from biolog-
ical oxidation. You should attempt to interpret the operating
10 100
9 90
8 80
Sulfide oxidised, t/d

7 70
Au recovery, %
6 60
5 50
4 40
3 30
2 S oxidised 20
1 10
Au
0 0
0 50 100
Feedrate, t/day
Figure 1.9 Typical biooxidation operating characteristics showing the effect of concentrate feed rate on the extent
of sulfide sulfur oxidized and gold recovered. Also shown are operating lines for 60% (____) and 85% (..)
oxidation.
diagram that shows two “operating” lines at 60% and 85% oxida-
tion. Note the effect of feed rate on the rate of oxidation of the sul-
fide and on the subsequent recovery of gold by cyanidation. Why
does the rate of sulfide oxidation decrease at a feed rate of greater
than about 55 t d1?
In both bioleaching (or biooxidation) and pressure leaching
processes, the rate-determining step can be the transfer of oxy-
gen from the gas phase to the liquid phase, and, as outlined in
Chapter 5 in Volume 1, this flux(j) of oxygen can be described
by the equation
j ¼ KL ðc co Þ (1.13)
in which c* ¼ po/H is the hypothetical liquid phase concentration

of the gas that would be in equilibrium with the bulk gas, co is the
bulk solution phase oxygen concentration, and k is the overall
mass transfer coefficient. po is the partial pressure of oxygen in
the gas phase, and H is the relevant Henry’s Law constant.
The rate equation for the transfer of oxygen can therefore be
written as
dc=dt ¼ ðkL A = VÞðc co Þ (1.14)
in which A is the area of the gas/liquid interface and V the volume

of the liquid phase.
This is often written as
dc=dt ¼ kL aðc co Þ (1.15)
in which a is the gas/liquid interfacial area per unit volume of the

liquid phase. This value can be easily measured by several
methods such as sparging a batch of deoxygenated pulp or solu-
tion with oxygen or air and recording the increase in the dis-
solved oxygen concentration as a function of time. A plot of the
data according to the previous first-order rate equation will yield
a value of kLa.
For most agitated reactors used for bio- or pressure oxidation,
the following empirical equation describes the effects of the rate
of addition of gas and the agitation on the rate constant (kLa).
b
kL a ¼ aðP=VÞ Ug (1.16)
in which a, b, and g are adjustable (positive) parameters. In many

cases, g ¼ 1 while the values of a and b depend on the type of
impellor and gas distribution system used. P/V is the impellor po-
wer per unit volume and U is the impellor tip speed.
Typical data are shown in Fig. 1.10 for a 300 m3 reactor fitted
with a flat-blade impellor and a sparging ring below the impellor.
1.7 Pressure leaching

Pressure leaching is generally applied when either
(i) the rate of oxidation or dissolution of a mineral is too slow at
temperatures below 90 C to make recovery economically
Figure 1.10 Performance of an agitated bioreactor in terms of gas dispersion.

viable. An example is the recovery of gold from refractory gold

ores containing pyrite or arsenopyrite.
(ii) selective dissolution of the valuable component(s) can be
achieved by operation at high temperatures. An example is
the leaching of nickel and cobalt from laterite ores in which
iron is precipitated as goethite or hematite.
This technology can be applied to many oxidation, reduction,
precipitation, and leaching processes. The number of applica-
tions is growing and includes
• Refractory golddacid and alkaline
• Nickel, cobalt, and copperdsulfides, mattes, and oxides
• Zincdsulfides
• Alumina
• Tungsten
• Uranium
The advantages of leaching at elevated temperatures are pri-
marily associated with greater kinetics and higher recoveries.
This enables oxygen to be used as an oxidant with obvious eco-
nomic advantages. Furthermore, iron is generally precipitated
as an oxide at high temperatures (Chapter 2 in Volume 1). The
additional energy requirements can be partially offset if heat is
efficiently recovered from the hot discharged slurry.
Disadvantages include the relatively high capital, operating,
and maintenance costs. In addition, pure oxygen is generally
required from an on-site oxygen plant. Except for iron, selectivity
generally decreases as the temperature increases. In many cases,
the leach slurry is generally moderately acidic and often highly
oxidizing, requiring specialized materials for autoclave and ancil-
laries fabrication. A photograph of a typical autoclave used for the
oxidation of gold concentrates is shown in Fig. 1.11.
Various pressure hydrometallurgical processes are now widely
used on a range of ores and concentrates with operating condi-
tions, which range up to 260 C and 5000 kPa. These plants have
convincingly demonstrated to the metallurgical industry that
pressure oxidation on a large scale (in excess of 2000 t/d of feed
per autoclave) is a reliable, efficient, and economic process. The
confidence developed within the industry as a result of the suc-
cessful large-scale application of pressure oxidation, particularly
in the gold industry, has led to the rapid expansion of the number
of operating and planned pressure acid leach plants. This, in turn,
will possibly result in the application of this technology in other
base metal areas, particularly copper.
The most significant advance in the recovery of zinc from pri-
mary concentrates has been the pressure-leach process devel-
oped in Canada and now used in a number of plants. It is
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Title: Peter Whiffle

His life and works
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Peter Whiffle
His Life and Works
BOOKS BY CARL VAN VECHTEN
INTERPRETERS
IN THE GARRET
THE MERRY-GO-ROUND
THE MUSIC OF SPAIN
THE TIGER IN THE HOUSE
MUSIC AND BAD MANNERS
LORDS OF THE HOUSETOPS
MUSIC AFTER THE GREAT WAR
PETER WHIFFLE: HIS LIFE AND WORKS
Peter Whiffle
His Life and Works

Carl Van Vechten
New York Alfred · A · Knopf
MCMXXIII
COPYRIGHT, 1922, BY
ALFRED A. KNOPF, Inc.
Published, April, 1922
Second Printing, April, 1922
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Eighth Printing, March, 1923
Ninth Printing, July, 1923
Set up, electrotyped, printed and bound by the Vail-Ballou Co., Binghamton, N.Y.
Paper furnished by W.F. Etherington & Co., New York.
MANUFACTURED IN THE UNITED STATES OF AMERICA

TO THE MEMORY OF
MY MOTHER,
ADA AMANDA FITCH VAN VECHTEN

"'Tingling is the test,' said Babbalanja, 'Yoomy,
did you tingle, when that song was
composing?'
"'All over, Babbalanja.'"
Herman Melville: Mardi.
"We work in the dark—we do what we can—
we give what we have. Our doubt is our
passion, and our passion is our task. The rest
is the madness of art."
Dencombe: The Middle Years.
"Les existences les plus belles sont peut-être
celles qui ont subi tous les extrêmes, qui ont
traversé toutes les températures, rencontré
toutes les sensations excessives et tous les
sentiments contradictoires."
Remy de Gourmont: Le Chat de Misère.
"The man who satisfies a ceaseless
intellectual curiosity probably squeezes more
out of life in the long run than any one else."
Edmund Gosse: Books on the Table.
"O mother of the hills, forgive our towers;
O mother of the clouds, forgive our
dreams."
Edwin Ellis.
Preface
So few people were acquainted with Peter Whiffle that the
announcement, on that page of the New York Times consecrated to
wedding, birth, and obituary notices, of his death in New York on
December 15, 1919, awakened no comment. Those of my friends
who knew something of the relationship between Peter and myself,
probably did not see the slender paragraph at all. At any rate none of
them mentioned it, save, of course, Edith Dale, whose interest, in a
sense, was as special as my own. Her loss was not so personal,
however, nor her grief so deep. It was strange and curious to
remember that however infrequently we had met, and the chronicle
which follows will give evidence of the comparative infrequency of
these meetings, yet some indestructible bond, a firm determining
girdle of intimate understanding, over which Time and Space had no
power, held us together. I had become to Peter something of a
necessity, in that through me he found the proper outlet for his
artistic explosions. I was present, indeed, at the bombing of more
than one discarded theory. It was under the spell of such apparently
trivial and external matters that our friendship developed and, while
my own interests often flew in other directions, Peter certainly
occupied as important a place in my heart as I did in his, probably, in
some respects, more important. Nevertheless, when I received a
notification from his lawyer that I had been mentioned in Peter's will,
I was considerably astonished. My astonishment increased when I
was informed of the nature of the bequest. Peter Whiffle had
appointed me to serve as his literary executor.
Now Peter Whiffle was not, in any accepted sense of the epithet, an
author. He had never published a book; he had never, indeed,
written a book. In the end he had come to hold a somewhat mystic
theory in regard to such matters, which he had only explained to me
a few moments before he died. I was, however, aware, more aware
than any one else could possibly have been, that from time to time
he had been accustomed to take notes. I was as familiar, I suppose,
as any one could be, with the trend of his later ideas, and with some
of the major incidents in his earlier life he had acquainted me,
although, here, I must confess, there were lacunæ in my knowledge.
Still, his testamentary request, unless I might choose to accept it in a
sense, I am convinced, entirely too flattering to my slender talents,
seemed to be inconsistent with the speculative idea which haunted
him, at least towards the end of his life. This contradiction and an
enlarging sense of the mysterious character of the assignment were
somewhat dispelled by a letter, dated June 17, 1917, which, a few
days after the reading of the will, his lawyer placed in my hands and
which indicated plainly enough that Peter had decided upon my
appointment at least two years and a half before he died. This letter
not only confirmed the strange clause in the will but also, to some
extent, explained it and, as the letter is an essential part of my
narrative, I offer it in evidence at once.
Dear Carl—so it read:
I suppose that some day I shall die; people do die. If there has been
one set purpose in my life, it has been not to have a purpose. That,
you alone, perhaps, understand. You know how I have always
hesitated to express myself definitely, you know how I have refrained
from writing, and you also know, perhaps, that I can write; indeed,
until recently, you thought I was writing, or would write. But I think
you realize now what writing has come to mean to me, definition,
constant definition, although it is as apparent as anything can be that
life, nature, art, whatever one writes about, are fluid and mutable
things, perpetually undergoing change and, even when they assume
some semblance of permanence, always presenting two or more
faces. There are those who are not appalled by these conditions,
those who confront them with bravery and even with impertinence.
You have been courageous. You have published several books
which I have read with varying shades of pleasure, and you have not
hesitated to define, or at any rate discuss, even that intangible,
invisible, and noisy art called Music.
I have begun many things but nothing have I ever completed. It has
always seemed unnecessary or impossible, although at times I have
tried to carry a piece of work through. On these occasions a
restraining angel has held me firmly back. It might be better if what I
have written, what I have said, were permitted to pass into oblivion
with me, to become a part of scoriac chaos. It may not mean
anything in particular; if it means too much, to that extent I have
failed.
Thinking, however, of death, as I sometimes do, I have wondered if,
after all, behind the vapoury curtain of my fluctuating purpose,
behind the orphic wall of my indecision, there did not lurk some
vague shadow of intention. Not on my part, perhaps, but on the part
of that being, or that condition, which is reported to be interested in
such matters. This doubt, I confess, I owe to you. Sometimes, in
those extraordinary moments between sleeping and awakening—
and once in the dentist's chair, after I had taken gas—the knots
seemed to unravel, the problem seemed as naked as Istar at the
seventh gate. But these moments are difficult, or impossible, to
recapture. To recapture them I should have been compelled to invent
a new style, a style as capricious and vibratory as the moments
themselves. In this, however, as you know, I have failed, while you
have succeeded. It is to your success, modest as it may appear to
you, that I turn in my dilemma. To come to the point, cannot you
explain, make out some kind of case for me, put me on my feet (or in
a book), and thereby prove or disprove something? Shameless as I
am, it would be inconceivable, absurd, for me to ask you to do this
while I am yet living and I have, therefore, put my request into a
formal clause in my will. After I am dead, you may search your
memory, which I know to be very good, for such examples of our
conversations as will best be fitted to illuminate your subject, which I
must insist—you, yourself, will understand this, too, sooner or later—
is not me at all.
When your book is published, I shall be dead and perhaps
unconscious. If, however, as I strongly suspect, some current
connects the life to be with the life that is, I can enjoy what you have
done. At the best, you may give others a slight intimation of the
meaning of inspiration or furnish guideposts, lighthouses, and bell-
buoys to the poet who intends to march singing along the highroad
or bravely to embark on the ships at sea; at the worst, I have
furnished you with a subject for another book, and I am well aware
that subjects even for bad books are difficult to light upon.
Salve atque Vale,
Peter.
This letter, I may say, astonished me. I think it would astonish
anybody. A profound and enveloping melancholy succeeded to this
feeling of astonishment. At the time, I was engaged in putting the
finishing touches to The Tiger in the House and I postponed
meditation on Peter's affair until that bulky volume could be
dispatched to the printer. That happy event fell on March 15, 1920,
but my anthology, Lords of The Housetops, next claimed my
attention, and then the new edition of Interpreters, for which I had
agreed to furnish a new paper, and the writing of this new paper
amused me very much, carrying my mind not only far away from
cats, which had been occupying it for a twelvemonth, but also away
from Peter's request. At last, Interpreters was ready for the printer,
but now the proofs of The Tiger began to come in, and I may say that
for the next three months my days were fully occupied in the
correction of proofs, for those of Lords of The Housetops and
Interpreters were in my garret when the proofs of The Tiger were not.
Never have I corrected proofs with so much concentrated attention
as that which I devoted to the proofs of The Tiger, and yet there were
errors. In regard to some of these, I was not the collaborator. On
Page 240, for instance, one may read, There are many females in
the novels of Emile Zola. My intention was to have the fourth word
read, felines, and so it stood in the final proof, but my ambition to
surmount the initial letter of Zola's Christian name with an acute
accent (an ambition I shall forswear on this present page), compelled
the printer to reset the line, so that subsequently, when I opened the
book at this page, I read with amazement that there are many
females in the novels of Emile Zola, a statement that cannot be
readily denied, to be sure, but still it is no discovery of which to
boast.
It was not until September, 1920, that I had an opportunity to
seriously consider Peter's request and when I did begin to consider
it, I thought of it at first only as a duty to be accomplished. But when I
began searching my memory for details of the conversations
between us and had perused certain notes I had made on various
occasions, visited his house on Beekman Place to look over his
effects and talk with his mother, the feeling of the artist for inevitable
material came over me and I knew that whether Peter had written
me that letter or not, I should sooner or later have written this book
about him.
There was another struggle over the eventual form, a question
concerning which Peter had made no suggestions. It seemed to me,
at first, that a sort of haphazard collection of his ideas and
pronunciamentos, somewhat in the manner of Samuel Butler's Note-
Books, would meet the case, but after a little reflection I rejected this
idea. Light on the man was needed for a complete understanding of
his ideas, or lack of them, for they shifted like the waves of the sea. I
can never tell why, but it was while I was reading William Dean
Howells's Familiar Spanish Studies one day in the New York Public
Library that I suddenly decided on a sort of loose biographical form,
a free fantasia in the manner of a Liszt Rhapsody. This settled, I
literally swam ahead and scarcely found it necessary to examine
many papers (which was fortunate as few exist) or to consult
anything but my memory, which lighted up the subject from obscure
angles, as a search-light illuminates the spaces of the sea, once I
had learned to decipher the meaning of the problem. What it is all
about, or whether it is about anything at all, you, the reader, of
course, must decide for yourself. To me, the moral, if I may use a
conventional word to express an unconventional idea, is plain, and if
I have not succeeded in making it appear so, then I must to some
extent blame you, the reader, for what is true of all books, is perhaps
truest of this, that you will carry away from it only what you are able
to bring to it.
Chapter I
One of my friends, a lady, visited Venice alone in her middle age. It
was late at night when the train drew into the station, and it was
raining, a drizzly, chilling rain. The porter pushed her, with her bag,
into a damp gondola and the dismal voyage to the hotel began.
There were a few lights here and there but she had the impression
that she was floating down the Chicago River in a wash-tub. Once
she had reached her destination, she clambered unsteadily out of
the black barge, wobbled through a dark passageway, inhaling great
whiffs of masticated garlic, and finally emerged in a dimly lighted
lobby. At the desk, a sleepy clerk yawned as she spoke of her
reservation. Tired, rather cross, and wholly disappointed, she
muttered, I don't like Venice at all. I wish I hadn't come. The clerk
was unsympathetically explanatory, Signora should have visited
Venice when she was younger.
A day or so later, the lady recovered her spirits and even her sense
of humour for she told me the story herself and I have always
remembered it. The moment it passed her lips, indeed, I began to
reflect that I had been lucky to encounter the Bride of the Adriatic in
my youth. Paris, too, especially Paris, for there is a melancholy
pleasure to be derived from Venice. It is a suitable environment for
grief; there is a certain superior relish to suffering there. Paris, I
sometimes think, smiles only on the very young and it is not a city I
should care to approach for the first time after I had passed forty.
I was, as a matter of fact, in my twenties when I first went to Paris—
my happiness might have been even greater had I been nineteen—
and I was alone. The trip across England—I had landed at Liverpool
—and the horrid channel, I will not describe, although both made
sufficient impression on me, but the French houses at Dieppe
awakened my first deep emotion and then, and so many times since,
the Normandy cider, quaffed in a little café, conterminous to the
railroad, and the journey through France, alive in the sunlight, for it
was May, the fields dancing with the green grain spattered with
vermilion poppies and cerulean cornflowers, the white roads, flying
like ribbons between the stately poplars, leading away over the
charming hills past the red-brick villas, completed the siege of my not
too easily given heart. There was the stately and romantic
interruption of Rouen, which at that period suggested nothing in the
world to me but Emma Bovary. Then more fields, more roads, more
towns, and at last, towards twilight, Paris.
Railroads have a fancy for entering cities stealthily through
backyards and the first glimpses of Paris, achieved from a car-
window, were not over-pleasant but the posters on the hoardings,
advertising beer and automobile tires, particularly that of the Michelin
Tire Company, with the picture of the pinguid gentleman, constructed
of a series of pneumatic circles, seemed characteristic enough.
Chéret was dead but something of his spirit seemed to glow in these
intensely coloured affiches and I was young. Even the dank Gare
Saint Lazare did not dismay me, and I entered into the novel
baggage hunt with something of zest, while other busy passengers
and the blue porters rushed hither and thither in a complicated but
well-ordered maze. Naturally, however, I was the last to leave the
station; as the light outside deepened to a rich warm blue, I
wandered into the street, my porter bearing my trunk, to find there a
solitary cocher mounted on the box of his carious fiacre.
An artist friend, Albert Worcester, had already determined my
destination and so I gave commands, Hotel de la Place de l'Odéon,
the cocher cracked his whip, probably adding a Hue cocotte! and we
were under way. The drive through the streets that evening seemed
like a dream and, even later, when the streets of Paris had become
more familiar to me than those of any other city, I could occasionally
recapture the mood of this first vision. For Paris in the May twilight is
very soft and exquisite, the grey buildings swathed in a bland blue
light and the air redolent with a strange fragrance, the ingredients of
which have never been satisfactorily identified in my nasal
imagination, although Huysmans, Zola, Symons, and Cunninghame
Graham have all attempted to separate and describe them.
Presently we crossed the boulevards and I saw for the first time the
rows of blooming chestnut trees, the kiosques where newsdealers
dispensed their wares, the brilliantly lighted theatres, the sidewalk
cafés, sprinkled with human figures, typical enough, doubtless, but
who all seemed as unreal to me at the time as if they had been
Brobdingnags, Centaurs, Griffins, or Mermaids. Other fiacres, private
carriages, taxi-autos, carrying French men and French ladies,
passed us. I saw Bel Ami, Nana, Liane de Pougy, or Otero in every
one of them. As we drove by the Opéra, I am certain that Cléo de
Mérode and Leopold of Belgium descended the steps. Even the
buses assumed the appearance of gorgeous chariots, bearing
perfumed Watteauesque ladies on their journey to Cythera. As we
drove through the Tuileries Gardens, the mood snapped for an
instant as I viewed the statue of Gambetta, which, I thought at the
time, and have always thought since, was amazingly like the portrait
of a gentleman hailing a cab. What could more completely symbolize
Paris than the statue of a gentleman perpetually hailing a cab and
never getting one?
We drove on through the Louvre and now the Seine was under us,
lying black in the twilight, reviving dark memories of crime and
murder, on across the Pont du Carrousel, and up the narrow Rue de
Seine. The Quartier Latin! I must have cried aloud, for the cocher
looked a trifle suspicious, his head turned the fraction of an inch.
Later, of course, I said, the left bank, as casually as any one. It was
almost dark when we drove into the open Place, flanked by the
Odéon, a great Roman temple, with my little hotel tucked into one
corner, as unostentatiously as possible, being exactly similar to
every other structure, save the central one, in the Place. I shall stop
tonight, I said to myself, in the hotel where Little Billee lived, for,
when one first goes to Paris when one is young, Paris is either the
Paris of Murger, du Maurier, or the George Moore of the
Confessions, perhaps the Paris of all three. In my bag these three
books lay, and I had already begun to live one of them.
The patron and a servant in a long white apron were waiting,
standing in the doorway. The servant hoisted my trunk to his
shoulder and bore it away. I paid the cocher's reckoning, not without
difficulty for, although I was not ignorant of the language, I was
unaccustomed to the simplicity of French coinage. There were also
the mysteries of the pourboire to compute—ten per cent, I had been
told; who has not been told this?—and besides, as always happens
when one is travelling, I had no little money. But at length the
negotiations were terminated, not to the displeasure of the cocher, I
feel certain, since he condescended to smile pleasantly. Then, with a
crack of his whip, this enormous fellow with his black moustaches,
his glazed top-hat, and his long coat, drove away. I cast a long
lingering look after him, apparently quite unaware that many another
such teratological specimen existed on every hand. Now I followed
the patron into a dark hallway and new strata of delight. He gave me
a lighted candle and, behind him, I mounted the winding stairway to
the first floor, where I was deposited in a chamber with dark red
walls, heavy dark red curtains at the windows, which looked out over
the Place, a black walnut wash-hand-stand with pitcher and basin, a
huge black walnut wardrobe, two or three chairs of the same wood,
upholstered with faded brocade, and a most luxurious bed, so high
from the floor that one had to climb into it, hung with curtains like
those at the window, and surmounted by a feather-bed. There was
also another article of furniture, indispensable to any French
bedroom.
I gave Joseph (all men servants in small hotels in Paris are named
Joseph, perhaps to warn off prospective Potiphar's wives) his vail,
asked for hot water, which he bore up promptly in a small can,
washed myself, did a little unpacking, humming the Mattchiche the
while, changed my shirt, my collar and my necktie, demanded
another bougie, lighted it, and under the humble illumination afforded
by it and its companion, I began to read again The Confessions of a
Young Man. It was not very long before I was interrupted in the midst
of an absorbing passage descriptive of the circle at the Nouvelle
Athènes by the arrival of Albert Worcester, who had arranged for my
reception, and right here I may say that I was lodged in the Hotel de
la Place de l'Odéon for fifty francs a month. Albert's arrival, although
unannounced, was not unexpected, as he had promised to take me
to dinner.
I was sufficiently emphatic. Paris! I cried. Paris! Good God!
I see you are not disappointed. But Albert permitted a trace of
cynicism to flavour his smile.
It's too perfect, too wonderful. It is more than I felt or imagined. I'm
moving in.
But you haven't seen it....
I've seen enough. I don't mean that. I mean I've seen enough to
know. But I want to see it all, everything, Saint Sulpice, the Folies-
Bergère, the Musée de Cluny, the Nouvelle Athènes, the Comédie
Française, the Bal Bullier, the Arc de Triomphe, the Luxembourg
Gardens....
They close at sundown. My expression was the cue for him to
continue, They'll be open tomorrow and any other day. They're just
around the corner. You can go there when you get up in the morning,
if you do get up in the morning. But what do you want to do tonight?
Anything! Everything! I cried.
Well, we'll eat first.
So we blew out the candles, floated down the dark stairs—I didn't
really walk for a week, I am sure—, brushing on our way against a
bearded student and a girl, fragrant and warm in the semi-blackness,
out into the delicious night, with the fascinating indescribable odour
of Paris, which ran the gamut from the fragrance of lilac and mimosa
to the aroma of horse-dung; with the sound of horses' hoofs and
rolling wheels beating and revolving on the cobble-stones, we made
our way—I swear my feet never touched the ground—through the
narrow, crooked, constantly turning, bewildering streets, until we
came out on a broad boulevard before the Café d'Harcourt, where I
was to eat my first Paris dinner.
The Café d'Harcourt is situated near the Church of the Sorbonne on
the Boulevard Saint Michel, which you are more accustomed to see
spelled Boul' Mich'. It is a big, brightly lighted café, with a broad
terrasse, partially enclosed by a hedge of green bushes in boxes.
The hands of the clock pointed to the hour of eight when we arrived
and the tables all appeared to be occupied. Inside, groups of men
were engaged in games of checkers, while the orchestra was

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3 Precipitation and crystallization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85

4 Solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117

5 Adsorption and ion exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171

5.9 Modeling of breakthrough. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203

6 Cementation and reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247

7 Electrowinning and electroreﬁning of metals. . . . . . . . . . . . . . . . . . . . . . 271

7.13 Electrowinning in novel cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362

8 Process selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395

1.1 Leaching methods

Heap (or dump) leaching: Lixiviant sprinkled over heaps of

Agitation leaching: Milled ore contacted with lixiviant in

Pressure leaching: Milled ore or concentrate contacted with lixi-

Bacterial leaching: A variation of heap or agitation leaching in

1.2 Typical leaching processes

In-Situ Heaps Crush Crush Crush

Vat Grind Grind

Months to Years Days Mins to hours

Increasing value of material leached

Figure 1.1 Selection of leaching method with grade of feed material.

and oxidative leaching as outlined in Chapter 6 in Volume 1. The

1.3 Batch leaching kinetics

Table 1.1 Some leaching processes in operation.

Feed Lixiviant Oxidant Temp. Pressure Equipment

rate-determining step is either mass transport or chemical reac-

in which [Au] is the concentration (mass gold/unit mass of pulp)

where [Au]o is the initial concentration. This equation can be writ-

in which k0 ¼ k([Au]o[Au]f) and X ¼ ([Au][Au]f)/([Au]o[Au]f) is

1.4 Continuous leachingdmicro- and

The analysis of the performance of this type of reactor de-

1.4.1 Residence time distribution in a CSTR

if the total vessel volume is V, each tank has volume Vi ¼ (V/N).

Figure 1.4 Residence time distributions for tanks in series.

Table 1.2 Fraction of ﬂuid with various residence times.

It is apparent that as the number of tanks increases, the distri-

Particle size, shape, reactivity

1.5 Counter-current leaching

1st Stage Leach, 50oC, pH 4

2nd Stage Leach, 80oC, 10 g/L acid Calcine, NH 4+

Figure 1.7 A three-stage counter-current leaching process for zinc calcine.

stage and (b) small amounts of spent electrolyte to control the pH

introduction of additional water for washing the ﬁlter cakes

1.6 Bacterial oxidation and leaching

• Use of microorganisms of which thiobacillus ferrooxidans and

14Fe2 D þ 7=2O2 þ 14Hþ ¼ 14Fe3þ D 7H2 O (1.7)

that is, overall,

acid is consumed and must be provided to keep the pH in the op-

On the other hand, there are some disadvantages such as

1.6.1 Process parameters for biological oxidation

Table 1.3 Reagent and power requirements.