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SECOND EDITION
ELECTROCHEMICAL
METHODS
Fundamentals and
Applications
Allen J. Bard
Larry R. Faulkner
Department of Chemistry and Biochemistry
University of Texas at Austin
JOHN WILEY & SONS, INC.

New Yorke Chichester • Weinheim
Brisbane e Singapore e Toronto
Major Symbols xi
Section
Symbol Meaning Usual Units References
Ещ equilibrium potential of an electrode V 1.3.2,3.4.1

EF Fermi level eV 2.2.5, 3.6.3
Em flat-band potential V 18.2.2
Eg bandgap of a semiconductor eV 18.2.2
E; initial potential V 6.2.1
Щ junction potential mV 2.3.4
Em membrane potential mV 2.4
EP peak potential V 6.2.2
A£P (a)|£pa-£pc|inCV V 6.5
(b) pulse height in SWV mV 7.3.5
Ep/2 potential where / = /p/2 in LSV V 6.2.2
£pa anodic peak potential V 6.5
£pc cathodic peak potential V 6.5
staircase step height in SWV mV 7.3.5
£Z potential of zero charge V 13.2.2
*л switching potential for cyclic voltammetry V 6.5
Еф quarter-wave potential in V 8.3.1
chronopotentiometry
E\I2 (a) measured or expected half-wave V 1.4.2,5.4,5.5
potential in voltammetry
(b) in derivations, the "reversible" V 5.4
half-wave potential,
Eo> + (RT/nF)\n(DR/D0)l/2
Ещ potential where i/i^ = 1 / 4 V 5.4.1
Е
Ъ1А potential where ///d = 3/4 V 5.4.1
e (a) electronic charge с
(b) voltage in an electric circuit V 10.1.1,15.1
e\ input voltage V 15.2
e0 output voltage V 15.1.1
voltage across the input terminals of an /xV 15.1.1
amplifier
ег%) error function of x none A.3
erfc(x) error function complement of x none A.3
F the Faraday constant; charge on one С
mole of electrons
f (a) F/RT V" 1
(b) frequency of rotation r/s 9.3
(c) frequency of a sinusoidal oscillation s- 1 10.1.2
(d) SWV frequency s- 1 7.3.5
(e) fraction titrated none 11.5.2
/(E) Fermi function none 3.6.3
fUk) fractional concentration of species / in none B.1.3
boxy after iteration к in a simulation
G Gibbs free energy kJ, kJ/mol 2.2.4
AG Gibbs free energy change in a chemical kJ, kJ/mol 2.1.2,2.1.3
process
G electrochemical free energy kJ, kJ/mol 2.2.4
G° standard Gibbs free energy kJ, kJ/mol 3.1.2
xii Major Symbols
Section
AG° standard Gibbs free energy change in a kJ, kJ/mol 2.1.2,2.1.3

chemical process
standard Gibbs free energy of activation kJ/mol 3.1.2
дс!transfer, j
j
standard free energy of transfer for kJ/mol 2.3.6
species j from phase a into phase /3
2
(a) gravitational acceleration cm/s
2 2
(b) interaction parameter in adsorption J-cm /mol 13.5.2
isotherms
H (a) enthalpy kJ, kJ/mol 2.1.2
-l/2
s 5.5.1
Mi enthalpy change in a chemical process kJ, kJ/mol 2.1.2
A#° standard enthalpy change in a chemical kJ, kJ/mol 2.1.2
process
standard enthalpy of activation kJ/mol 3.1.2
Planck constant J-s
corrected mercury column height at a DME cm 7.1.4
/ amplitude of an ac current A 10.1.2
/(0 convolutive transform of current; C/s1/2 6.7.1
semi-integral of current
/ current phasor A 10.1.2
7 diffusion current constant for average Â-s1/2/(mg2/3-mM) 7.1.3
current
diffusion current constant for maximum M-s 1/2 /(mg 2/3 -mM) 7.1.3
current
peak value of ac current amplitude A 10.5.1
current A 1.3.2
А/ difference current in SWV = if — ir A 7.3.5
8i difference current in DPV = /(r) - Z(r') A 7.3.4
/(0) initial current in bulk electrolysis A 11.3.1
*А characteristic current describing flux of the A 14.4.2
primary reactant to a modified RDE
anodic component current A 3.2
(a) charging current A 6.2.4
(b) cathodic component current A 3.2
(a) current due to diffusive flux A 4.1
(b) diffusion-limited current A 5.2.1
average diffusion-limited current flow A
7.1.2
over a drop lifetime at a DME
Od)max diffusion-limited current at tm.dX at a A
7.1.2
DME (maximum current)
characteristic current describing diffusion A
14.4.2
of electrons within the film at a
modified electrode
(a) faradaic current A
(b) forward current A 5.7
kinetically limited current A 9.3.4
characteristic current describing A 14.4.2
cross-reaction within the film at a
modified electrode
Major Symbols xui
Section
Ч limiting current A 1.4.2

k& limiting anodic current A 1.4.2
kc limiting cathodic current A 1.4.2
migration current A 4.1
h characteristic current describing A 14.4.2
permeation of the primary reactant
into the film at a modified electrode
>P peak current A 6.2.2
'pa anodic peak current A 6.5.1
*pc cathodic peak current A 6.5.1
'r current during reversal step A 5.7
'S (a) characteristic current describing A 14.4.2
diffusion of the primary reactant
through the film at a modified electrode
(b) substrate current in SECM A 16.4.4
4s steady-state current A 5.3
h tip current in SECM A • 16.4.2
*T,oo tip current in SECM far from the A 16.4.1
substrate
h exchange current A 3.4.1,3.5.4
*0,t true exchange current A 13.7.1
Im(w) imaginary part of complex function w A.5
/jfe t) flux of species j at location x at time t mol c m " 2 s" 1 1.4.1,4.1
j (a) current density A/cm2 1.3.2
(b) box index in a simulation none B.1.2
(c)VÎ none A.5
h exchange current density A/cm 3.4.1,3.5.4
К equilibrium constant none
precursor equilibrium constant for depends on case 3.6.1
reactant j
к (a) rate constant for a homogeneous depends on order
reaction
(b) iteration number in a simulation none B.I
(c) extinction coefficient none 17.1.2
Boltzmann constant J/K
k° standard heterogeneous rate constant cm/s 3.3, 3.4
К (a) heterogeneous rate constant for cm/s 3.2
oxidation
(b) homogeneous rate constant for depends on order 3.1
"backward" reaction
kf (a) heterogeneous rate constant for cm/s 3.2
reduction
(b) homogeneous rate constant for depends on order 3.1
"forward" reaction
*?? potentiometric selectivity coefficient of
interferenty toward a measurement
none 2.4
of species /
k° true standard heterogeneous rate cm/s 13.7.1
constant
xiv Major Symbols
Section
L length of a porous electrode 11.6.2

L{f(t)} Laplace transform of/(0 = f(s) A.I
L~]{f(s)} inverse Laplace transform of f(s) A.I
I thickness of solution in a thin-layer cell cm 11.7.2
€ number of iterations corresponding to t^ none B.1.4
in a simulation
m mercury flow rate at a DME mg/s 7.1.2
1/2
m(t) convolutive transform of current; C/s 6.7.1
semi-integral of current
m-} mass-transfer coefficient of species j cm/s 1.4.2
N collection efficiency at an RRDE none 9.4.2
3
NA (a) acceptor density cm" 18.2.2
1
(b) Avogadro's number тоГ
3
ND donor density cm" 18.2.2
iVj total number of moles of species j in mol 11.3.1
a system
n (a) stoichiometric number of electrons none 1.3.2
involved in an electrode reaction
cm" 3 18.2.2
(b) electron density in a semiconductor
none 17.1.2
(c) refractive index
none 17.1.2
n complex refractive index
cm" 3 13.3.2
n° number concentration of each ion in a
z: z electrolyte
cm" 3 18.2.2
щ electron density in an intrinsic
semiconductor
mol 2.2.4, 13.1.1
щ (a) number of moles of species у in a phase
cm" 3 13.3.2
(b) number concentration of ion у in an
electrolyte -3
cm 13.3.2
n® number concentration of ion у in the bulk
electrolyte
О oxidized form of the standard system
О + ne ^ R; often used as a subscript
denoting quantities pertaining to
species О
P pressure Pa, atm
cm" 3 18.2.2
p (a) hole density in a semiconductor
s" 1 11.3.1
(b) mjA/V
P\ hole density in an intrinsic semiconductor cm" 3 18.3.2
Q charge passed in electrolysis С 1.3.2,5.8.1, 11.3.1
<2° charge required for complete electrolysis С 11.3.4
of a component by Faraday's law
gd chronocoulometric charge from a с 5.8.1
diffusing component
Qdi charge devoted to double-layer с 5.8
capacitance
cf excess charge on phase у СдС 1.2,2.2
R reduced form of the standard system,
О + ne i=^ R; often used as a subscript
denoting quantities pertaining to
species R
Major Symbols xv
Section
R (a) gas constant Jmol^K"
1
(b) resistance ft 10.1.2

(c) fraction of substance electrolyzed in none 11.6.2
a porous electrode
(d) reflectance none 17.1.2
RB series equivalent resistance of a cell ft 10.4
Ret charge-transfer resistance ft 1.3.3,3.4.3
R{ feedback resistance a 15.2
Rmt mass-transfer resistance ft 1.4.2,3.4.6
Rs (a) solution resistance ft 1.3.4
(b) series resistance in an equivalent ft 1.2.4, 10.1.3
circuit
Ru uncompensated resistance ft 1.3.4, 15.6
Ra ohmic solution resistance ft 10.1.3
r radial distance from the center of an cm 5.2.2,5.3,9.3.1
electrode
rc radius of a capillary cm 7.1.3
fo radius of an electrode cm 5.2.2, 5.3
r\ radius of the disk in an RDE or RRDE cm 9.3.5
Г2 inner radius of a ring electrode cm 9.4.1
гъ outer radius of a ring electrode cm 9.4.1
Re Reynolds number none 9.2.1
Re(w) real part of complex function w A.5
AS entropy change in a chemical process kJ/K.kJmol^K"1 2.1.2
AS0 standard entropy change in a chemical kJ/K.kJmol^K"1 2.1.2
process
AS* standard entropy of activation kJmol^K"1 3.1.2
Sr(t) unit step function rising at t = т none A. 1.7
s (a) Laplace plane variable, usually A.I
complementary to t
1
(b) specific area of a porous electrode cm" 11.6.2
T absolute temperature К
t time s
4 transference number of species у none 2.3.3, 4.2
known characteristic time in a simulation s B.1.4
чтшх drop time at a DME s 7.1.2
'p
pulse width in SWV s 7.3.5
Щ mobility of ion (or charge carrier) j cn^V'V1 2.3.3,4.2
V volume cm 3
V (a) linear potential scan rate V/s 6.1
(b) homogeneous reaction rate mol cm" 3 s~l 1.3.2,3.1
(c) heterogeneous reaction rate mol cm" 2 s" 1 1.3.2, 3.2
(d) linear velocity of solution flow, usually cm/s 1.4.1,9.2
a function of position
vh (a) "backward" homogeneous reaction rate mol cm~ 3 s" 1 3.1
(b) anodic heterogeneous reaction rate mol c m " 2 s-1 3.2
Vf (a) "forward" homogeneous reaction rate mol cm" 3 s" 1 3.1
(b) cathodic heterogeneous reaction rate mol cm" 2 s~] 3.2
V\ component of velocity in the j direction cm/s 9.2.1
xvi Major Symbols
Section
2
*>mt rate of mass transfer to a surface mol cm s ' 1.4.1
1
Wj(A,E) probability density function for species j eV" 3.6.3
w width of a band electrode cm 5.3
Wj work term for reactant j in electron eV 3.6.2
transfer
*c capacitive reactance n 10.1.2
x mole fraction of species j none 13.1.2
>
X distance, often from a planar electrode cm
X\ distance of the IHP from the electrode cm 1.2.3, 13.3.3
surface
x2 distance of the OHP from the electrode cm 1.2.3, 13.3.3
surface
Y admittance rr1 1
10.1.2
Y admittance vector ft" 10.1.2
У distance from an RDE or RRDE cm 9.3.1
z (a) impedance n 10.1.2
(b) dimensionless current parameter in none B.1.6
simulation
z impedance vector ft 10.1.2
faradaic impedance ft 10.1.3
Z\m imaginary part of impedance a 10.1.2
^Re real part of impedance ft 10.1.2
7 Warburg impedance ft 10.1.3
z (a) distance normal to the surface of a cm 5.3
disk electrode or along a cylindrical
electrode
(b) charge magnitude of each ion in a none 13.3.2
z: z electrolyte
Z
j
charge on species j in signed units of none 2.3
electronic charge
GREEK SYMBOLS
Section
(a) transfer coefficient none 3.3

(b) absorption coefficient cm"1 17.1.2
(a) distance factor for extended charge A"1 3.6.4
transfer
(b) geometric parameter for an RRDE none 9.4.1
(c) 1 - a none 10.5.2
(a) дЕ/дС}(0, t) V-cm3/mol 10.2.2
(b) equilibrium parameter in an adsorption none 13.5.2
isotherm for species у
surface excess of species j at equilibrium mol/cm2 13.1.2
relative surface excess of species у with mol/cm2 13.1.2
respect to component r
Major Symbols xvii
Section
2
surface excess of species j at saturation mol/cm 13.5.2
(a) surface tension dyne/cm
(b) dimensionless parameter used to define none 5.4.2, 5.5.2
frequency (time) regimes in step
experiments at spherical electrodes
П activity coefficient for species у none 2.1.5
Д ellipsometric parameter none 17.1.2
l/2
8 r0(s/Do) , used to define diffusional none 5.5.2
regimes at a spherical electrode
"diffusion" layer thickness for species у at 1.4.2,9.3.2
an electrode fed by convective transfer
(a) dielectric constant none 13.3.1
(b) optical-frequency dielectric constant none 17.1.2
(c) porosity none 11.6.2
complex optical-frequency dielectric none 17.1.2
constant
molar absorptivity of species у M" 1 cm " 1 17.1.1
]
permittivity of free space m"2 13.3.1
zeta potential mV 9.8.1
overpotential, E — Eeq V 1.3.2,3.4.2
charge-transfer overpotential V 1.3.3, 3.4.6
1
viscosity of fluid у gem' " V = poise 9.2.2
mass-transfer overpotential V 1.3.3, 3.4.6
none 5.4.1
s 1/2 5.8.2
fractional coverage of an interface by none 13.5.2
species у
(a) conductivity of a solution = fl" 1 -i
(b) transmission coefficient of a reaction none 3.1.3

(c) r0kf/Do, used to define kinetic regimes none 5.5.2
at a spherical electrode
(d) double-layer thickness parameter cm" 1 13.3.2
(e) partition coefficient for the primary none 14.4.2
reactant in a modified electrode system
electronic transmission coefficient none 3.6
1
A equivalent conductivity of a solution c m 2 ! ! " 1 equiv " 2.3.3
A (a) reorganization energy for electron eV 3.6
transfer
(b) £fr1/2(l + £0)/£>o2 none 5.5.1
(c) dimensionless homogeneous kinetic none 12.3
parameter, specific to a method and
mechanism
(d) switching time in CV s 6.5
(e) wavelength of light in vacuo nm 17.1.2
inner component of the reorganization eV 3.6.2
energy
equivalent ionic conductivity for ion у cm 2 II 1 equiv ] 2.3.3
equivalent ionic conductivity of ion у cm 2 fl" 1 equiv" 1 2.3.3
extrapolated to infinite dilution
xviii Major Symbols
Section
outer component of the reorganization eV 3.6.2

energy
(a) reaction layer thickness cm 1.5.2, 12.4.2
(b) magnetic permeability none 17.1.2
electrochemical potential of electrons in kJ/mol 2.2.4, 2.2.5
К
phase a
electrochemical potential of species j in kJ/mol 2.2.4
phase a
chemical potential of species у in phase a kJ/mol 2.2.4
standard chemical potential of species j in kJ/mol 2.2.4
phase a
(a) kinematic viscosity cm2/s 9.2.2
(b) frequency of light
stoichiometric coefficient for species у in a none 2.1.5
chemical process
s" 1 3.6
nuclear frequency factor
none 5.4.1
(D0/DR)112
fl-cm 4.2
(a) resistivity
(b) roughness factor none 5.2.3
p(E) electronic density of states cm 2 eV" 1 3.6.3
(a) nFv/RT s" 1 6.2.1
(b) (1MFAV2)[/3O/£>O/2 " J3R/£>R2] 10.2.3
excess charge density on phase у C/cm2 1.2,2.2
parameter describing potential dependence none 13.3.4
of adsorption energy
(a) transition time in chronopotentiometry s 8.2.2
(b) sampling time in sampled-current s 5.1,7.3
voltammetry
(c) forward step duration in a double-step 5.7.1
experiment
(d) generally, a characteristic time defined
by the properties of an experiment
(e) in treatments of UMEs, 4Dot/rl none 5.3
start of potential pulse in pulse voltammetry s 7.3
longitudinal relaxation time of a solvent s 3.6.2
Ф work function of a phase eV 3.6.4
Ф (a) electrostatic potential V 2.2.1
(b) phase angle between two sinusoidal degrees, 10.1.2
signals radians
(c) phase angle between / a c and £ a c degrees, 10.1.2
radians
(d) film thickness in a modified electrode cm 14.4.2
(a) electrostatic potential difference V 2.2
between two points or phases
(b) potential drop in the space charge 18.2.2
region of a semiconductor
absolute electrostatic potential of phase j V 2.2.1
junction potential at a liquid-liquid interface V 6.8
Major Symbols xix
Section
standard Galvani potential of ion transfer V 6.8
for species j from phase a to phase /3
Фо total potential drop across the solution side mV 13.3.2
of the double layer
ф2 potential at the OHP with respect to bulk V 1.2.3, 13.3.3
solution
X (12/7)1/2£fT1/2/Do/2 none 7.2.2
XU) dimensionless distance of box; in a none B.1.5
simulation
x
(bt) normalized current for a totally irreversible none 6.3.1
system in LSV and CV
x
(at) normalized current for a reversible system in none 6.2.1
LSV and CV
Xf rate constant for permeation of the primary cm/s 14.4.2
reactant into the film at a modified
electrode
Ф (a) ellipsometric parameter none 17.1.2
(b) dimensionless rate parameter in CV none 6.5.2
(a) angular frequency of rotation; s" 1 9.3
2тг X rotation rate
(b) angular frequency of a sinusoidal s" 1 10.1.2
oscillation; 2rrf
STANDARD ABBREVIATIONS
Section
Abbreviation Meaning Reference
ADC analog-to-digital converter 15.8

AES Auger electron spectrometry 17.3.3
AFM atomic force microscopy 16.3
ASV anodic stripping voltammetry 11.8
BV Butler- Volmer 3.3
CB conduction band 18.2.2
CE homogeneous chemical process preceding heterogeneous 12.1.1
electron transfer1
CV cyclic voltammetry 6.1,6.5
CZE capillary zone electrophoresis 11.6.4
DAC digital-to-analog converter 15.8
DME (a) dropping mercury electrode 7.1.1
(b) 1,2-dimethoxyethane
DMF TV, TV-dimethylformamide
DMSO Dimethylsulfoxide
DPP differential pulse polarography 7.3.4
DPV differential pulse voltammetry 7.3.4
betters may be subscripted i, q, or r to indicate irreversible, quasi-reversible, or reversible reactions.

xx Major Symbols
Section
EC heterogeneous electron transfer followed by homogeneous 12.1.1

1
chemical reaction
EC' catalytic regeneration of the electroactive species in a following 12.1.1
1
homogeneous reaction
ECE heterogeneous electron transfer, homogeneous chemical reaction, 12.1.1
and heterogeneous electron transfer, in sequence
ECL electrogenerated chemiluminescence 18.1
ECM electrocapillary maximum 13.2.2
ЕЕ step wise heterogeneous electron transfers to accomplish a 12.1.1
2-electron reduction or oxidation of a species
EIS electrochemical impedance spectroscopy 10.1.1
emf electromotive force 2.1.3
EMIRS electrochemically modulated infrared reflectance spectroscopy 17.2.1
ESR electron spin resonance 17.4.1
ESTM electrochemical scanning tunneling microscopy 16.2
EXAFS extended X-ray absorption fine structure 17.6.1
FFT fast Fourier transform A.6
GCS Gouy-Chapman-Stern 13.3.3
GDP galvanostatic double pulse 8.6
HCP hexagonal close-packed 13.4.2
HMDE hanging mercury drop electrode 5.2.2
HOPG highly oriented pyrolytic graphite 13.4.2
IHP inner Helmholtz plane 1.2.3, 13.3.3
IPE ideal polarized electrode 1.2.1
IRRAS infrared reflection absorption spectroscopy 17.2.1
IR-SEC infrared spectroelectrochemistry 17.2.1
ISE ion-selective electrode 2.4
ITIES interface between two immiscible electrolyte solutions 6.8
ITO indium-tin oxide thin film 18.2.5
LB Langmuir-Blodgett 14.2.1
LCEC liquid chromatography with electrochemical detection 11.6.4
LEED low-energy electron diffraction 17.3.3
LSV linear sweep voltammetry 6.1
MFE mercury film electrode 11.8
NHE normal hydrogen electrode = SHE 1.1.1
NCE normal calomel electrode, Hg/Hg2Cl2/KCl (1.0M)
NPP normal pulse polarography 7.3.2
NPV normal pulse voltammetry 7.3.2
OHP outer Helmholtz plane 1.2.3, 13.3.3
OTE optically transparent electrode 17.1.1
OTTLE optically transparent thin-layer electrode 17.1.1
PAD pulsed amperometric detection 11.6.4
PC propylene carbonate
PDIRS potential difference infrared spectroscopy 17.2.1
PZC potential of zero charge 13.2.2
QCM quartz crystal microbalance 17.5
1
Letters may be subscripted /, q, or r to indicate irreversible, quasi-reversible, or reversible reactions.
Major Symbols xxi
Section
QRE quasi-reference electrode 2.1.7
RDE rotating disk electrode 9.3
RDS rate-determining step 3.5
RPP reverse pulse polarography 7.3.4
RPV reverse pulse voltammetry 7.3.4
RRDE rotating ring-disk electrode 9.4.2
SAM self-assembled monolayer 14.2.2
SCE saturated calomel electrode 1.1.1
SECM scanning electrochemical microscopy 16.4
SERS surface enhanced Raman spectroscopy 17.2.2
SHE standard hydrogen electrode = NHE 1.1.1
SHG second harmonic generation 17.1.5
SMDE static mercury drop electrode 7.1.1
SNIFTIRS subtractively normalized interfacial Fourier transform infrared 17.2.1
spectroscopy
SPE solid polymer electrolyte 14.2.6
SPR surface plasmon resonance 17.1.3
SSCE sodium saturated calomel electrode, Hg/Hg2Cl2/NaCl (sat'd)
STM scanning tunneling microscopy 16.2
swv square wave voltammetry 7.3.5
TBABF4 tetra-/2-butylammonium fluoborate
TBAI tetra-ft-butylammonium iodide
TBAP tetra-w-butylammoniumperchlorate
TEAP tetraethylammonium perchlorate
THF tetrahydrofuran
UHV ultrahigh vacuum 17.3
UME ultramicroelectrode 5.3
UPD underpotential deposition 11.2.1
XPS X-ray photoelectron spectrometry 17.3.2
VB valence band 18.2.2
CHAPTER
1
INTRODUCTION
AND OVERVIEW
OF ELECTRODE
PROCESSES
1.1 INTRODUCTION
Electrochemistry is the branch of chemistry concerned with the interrelation of electri-
cal and chemical effects. A large part of this field deals with the study of chemical
changes caused by the passage of an electric current and the production of electrical en-
ergy by chemical reactions. In fact, the field of electrochemistry encompasses a huge
array of different phenomena (e.g., electrophoresis and corrosion), devices (elec-
trochromic displays, electro analytical sensors, batteries, and fuel cells), and technolo-
gies (the electroplating of metals and the large-scale production of aluminum and
chlorine). While the basic principles of electrochemistry discussed in this text apply to
all of these, the main emphasis here is on the application of electrochemical methods to
the study of chemical systems.
Scientists make electrochemical measurements on chemical systems for a variety of
reasons. They may be interested in obtaining thermodynamic data about a reaction. They
may want to generate an unstable intermediate such as a radical ion and study its rate of
decay or its spectroscopic properties. They may seek to analyze a solution for trace
amounts of metal ions or organic species. In these examples, electrochemical methods are
employed as tools in the study of chemical systems in just the way that spectroscopic
methods are frequently applied. There are also investigations in which the electrochemi-
cal properties of the systems themselves are of primary interest, for example, in the design
of a new power source or for the electrosynthesis of some product. Many electrochemical
methods have been devised. Their application requires an understanding of the fundamen-
tal principles of electrode reactions and the electrical properties of electrode-solution in-
terfaces.
In this chapter, the terms and concepts employed in describing electrode reactions
are introduced. In addition, before embarking on a detailed consideration of methods
for studying electrode processes and the rigorous solutions of the mathematical equa-
tions that govern them, we will consider approximate treatments of several different
types of electrode reactions to illustrate their main features. The concepts and treat-
ments described here will be considered in a more complete and rigorous way in later
chapters.
2 • Chapter 1. Introduction and Overview of Electrode Processes
1.1.1 Electrochemical Cells and Reactions

In electrochemical systems, we are concerned with the processes and factors that affect
the transport of charge across the interface between chemical phases, for example, be-
tween an electronic conductor (an electrode) and an ionic conductor (an electrolyte).
Throughout this book, we will be concerned with the electrode/electrolyte interface and
the events that occur there when an electric potential is applied and current passes. Charge
is transported through the electrode by the movement of electrons (and holes). Typical
electrode materials include solid metals (e.g., Pt, Au), liquid metals (Hg, amalgams), car-
bon (graphite), and semiconductors (indium-tin oxide, Si). In the electrolyte phase,
charge is carried by the movement of ions. The most frequently used electrolytes are liq-
+ +
uid solutions containing ionic species, such as, H , Na , Cl~, in either water or a non-
aqueous solvent. To be useful in an electrochemical cell, the solvent/electrolyte system
must be of sufficiently low resistance (i.e., sufficiently conductive) for the electrochemi-
cal experiment envisioned. Less conventional electrolytes include fused salts (e.g., molten
NaCl-KCl eutectic) and ionically conductive polymers (e.g., Nation, polyethylene
oxide-LiClO4). Solid electrolytes also exist (e.g., sodium j8-alumina, where charge is car-
ried by mobile sodium ions that move between the aluminum oxide sheets).
It is natural to think about events at a single interface, but we will find that one cannot
deal experimentally with such an isolated boundary. Instead, one must study the proper-
ties of collections of interfaces called electrochemical cells. These systems are defined
most generally as two electrodes separated by at least one electrolyte phase.
In general, a difference in electric potential can be measured between the electrodes in
an electrochemical cell. Typically this is done with a high impedance voltmeter. This cell
potential, measured in volts (V), where 1 V = 1 joule/coulomb (J/C), is a measure of the
energy available to drive charge externally between the electrodes. It is a manifestation of
the collected differences in electric potential between all of the various phases in the cell.
We will find in Chapter 2 that the transition in electric potential in crossing from one con-
ducting phase to another usually occurs almost entirely at the interface. The sharpness of
the transition implies that a very high electric field exists at the interface, and one can ex-
pect it to exert effects on the behavior of charge carriers (electrons or ions) in the interfa-
cial region. Also, the magnitude of the potential difference at an interface affects the
relative energies of the carriers in the two phases; hence it controls the direction and
the rate of charge transfer. Thus, the measurement and control of cell potential is one of the
most important aspects of experimental electrochemistry.
Before we consider how these operations are carried out, it is useful to set up a short-
hand notation for expressing the structures of cells. For example, the cell pictured in Fig-
ure 1.1.1a is written compactly as
Zn/Zn 2 + , СГ/AgCl/Ag (l.l.l)
In this notation, a slash represents a phase boundary, and a comma separates two compo-
nents in the same phase. A double slash, not yet used here, represents a phase boundary
whose potential is regarded as a negligible component of the overall cell potential. When
a gaseous phase is involved, it is written adjacent to its corresponding conducting ele-
ment. For example, the cell in Figure 1.1.1ft is written schematically as
Pt/H2/H+, СГ/AgCl/Ag (1.1.2)
The overall chemical reaction taking place in a cell is made up of two independent
half-reactions, which describe the real chemical changes at the two electrodes. Each half-
reaction (and, consequently, the chemical composition of the system near the electrodes)
1.1 Introduction 3
Pt H2
Zn Ag
СГ СГ
j
Excess Excess
AgCI AgCI
(а) (Ь)
Figure l.l.l Typical electrochemical cells, (a) Zn metal and Ag wire covered with AgCI immersed
in a ZnCl2 solution, (b) Pt wire in a stream of H2 and Ag wire covered with AgCI in HC1 solution.
responds to the interfacial potential difference at the corresponding electrode. Most of the
time, one is interested in only one of these reactions, and the electrode at which it occurs
is called the working (or indicator) electrode. To focus on it, one standardizes the other
half of the cell by using an electrode (called a reference electrode) made up of phases
having essentially constant composition.
The internationally accepted primary reference is the standard hydrogen electrode
(SHE), or normal hydrogen electrode (NHE), which has all components at unit activity:
Pt/H2(a - l)/H + (a = 1, aqueous) (1.1.3)
Potentials are often measured and quoted with respect to reference electrodes other than
the NHE, which is not very convenient from an experimental standpoint. A common ref-
erence is the saturated calomel electrode (SCE), which is
Hg/Hg2Cl2/KCl (saturated in water) (1.1.4)
Its potential is 0.242 V vs. NHE. Another is the silver-silver chloride electrode,
Ag/AgCl/KCl (saturated in water) (1.1.5)
with a potential of 0.197 V vs. NHE. It is common to see potentials identified in the litera-
ture as "vs. Ag/AgQ" when this electrode is used.
Since the reference electrode has a constant makeup, its potential is fixed. Therefore,
any changes in the cell are ascribable to the working electrode. We say that we observe or
control the potential of the working electrode with respect to the reference, and that is
equivalent to observing or controlling the energy of the electrons within the working elec-
trode (1, 2). By driving the electrode to more negative potentials (e.g., by connecting a
battery or power supply to the cell with its negative side attached to the working elec-
trode), the energy of the electrons is raised. They can reach a level high enough to transfer
into vacant electronic states on species in the electrolyte. In that case, a flow of electrons
from electrode to solution (a reduction current) occurs (Figure 1.1.2a). Similarly, the en-
ergy of the electrons can be lowered by imposing a more positive potential, and at some
point electrons on solutes in the electrolyte will find a more favorable energy on the elec-
trode and will transfer there. Their flow, from solution to electrode, is an oxidation cur-
rent (Figure 1.1.2b). The critical potentials at which these processes occur are related to
the standard potentials, E°, for the specific chemical substances in the system.
4 Chapter 1. Introduction and Overview of Electrode Processes
Electrode Solution Electrode Solution
Vacant
0 MO
Potential
Energy level
of electrons
0j Occupied
MO
A + e —> A
(a)
Electrode Solution Electrode Solution
Vacant
0 Energy level
MO
of electrons
Potential
0l Occupied
MO
A - e -^ A+
(b)
Figure 1.1.2 Representation of (a) reduction and (b) oxidation process of a species, A, in
solution. The molecular orbitals (MO) of species A shown are the highest occupied MO and the
lowest vacant MO. These correspond in an approximate way to the E°s of the A/A~ and A + /A
couples, respectively. The illustrated system could represent an aromatic hydrocarbon (e.g.,
9,10-diphenylanthracene) in an aprotic solvent (e.g., acetonitrile) at a platinum electrode.
Consider a typical electrochemical experiment where a working electrode and a ref-

erence electrode are immersed in a solution, and the potential difference between the elec-
trodes is varied by means of an external power supply (Figure 1.1.3). This variation in
potential, £, can produce a current flow in the external circuit, because electrons cross the
electrode/solution interfaces as reactions occur. Recall that the number of electrons that
cross an interface is related stoichiometrically to the extent of the chemical reaction (i.e.,
to the amounts of reactant consumed and product generated). The number of electrons is
measured in terms of the total charge, Q, passed in the circuit. Charge is expressed in
units of coulombs (C), where 1 С is equivalent to 6.24 X 10 1 8 electrons. The relationship
between charge and amount of product formed is given by Faraday's law; that is, the pas-
sage of 96,485.4 С causes 1 equivalent of reaction (e.g., consumption of 1 mole of reac-
tant or production of 1 mole of product in a one-electron reaction). The current, /, is the
rate of flow of coulombs (or electrons), where a current of 1 ampere (A) is equivalent to 1
C/s. When one plots the current as a function of the potential, one obtains a current-poten-
tial (i vs. E) curve. Such curves can be quite informative about the nature of the solution
and the electrodes and about the reactions that occur at the interfaces. Much of the re-
mainder of this book deals with how one obtains and interprets such curves.
1.1 Introduction 5
Power
supply
-Ag
Pt
-AgBr
Figure 1.1.3 Schematic diagram of the
electrochemical cell Pt/HBr(l M)/AgBr/Ag attached
to power supply and meters for obtaining a current-
1МНВГ
potential (i-E) curve.
Let us now consider the particular cell in Figure 1.1.3 and discuss in a qualitative
way the current-potential curve that might be obtained with it. In Section 1.4 and in later
chapters, we will be more quantitative. We first might consider simply the potential we
would measure when a high impedance voltmeter (i.e., a voltmeter whose internal resis-
tance is so high that no appreciable current flows through it during a measurement) is
placed across the cell. This is called the open-circuit potential of the cell.1
For some electrochemical cells, like those in Figure 1.1.1, it is possible to calculate
the open-circuit potential from thermodynamic data, that is, from the standard potentials
of the half-reactions involved at both electrodes via the Nernst equation (see Chapter 2).
The key point is that a true equilibrium is established, because a pair of redox forms
linked by a given half-reaction (i.e., a redox couple) is present at each electrode. In Figure
1.1.1/?, for example, we have H + and H 2 at one electrode and Ag and AgCl at the other.2
The cell in Figure 1.1.3 is different, because an overall equilibrium cannot be estab-
lished. At the Ag/AgBr electrode, a couple is present and the half-reaction is
AgBr + e ±± Ag + Br = 0.0713 Vvs. NHE (1.1.6)
Since AgBr and Ag are both solids, their activities are unity. The activity of Br can be
found from the concentration in solution; hence the potential of this electrode (with re-
spect to NHE) could be calculated from the Nernst equation. This electrode is at equilib-
rium. However, we cannot calculate a thermodynamic potential for the Pt/H+,Br~
electrode, because we cannot identify a pair of chemical species coupled by a given half-
reaction. The controlling pair clearly is not the H2,H+ couple, since no H 2 has been intro-
duced into the cell. Similarly, it is not the O 2 ,H 2 O couple, because by leaving O 2 out of
the cell formulation we imply that the solutions in the cell have been deaerated. Thus, the
Pt electrode and the cell as a whole are not at equilibrium, and an equilibrium potential
*In the electrochemical literature, the open-circuit potential is also called the zero-current potential or the rest
potential.
2
When a redox couple is present at each electrode and there are no contributions from liquid junctions (yet to be
discussed), the open-circuit potential is also the equilibrium potential. This is the situation for each cell in
Figure 1.1.1.
Chapter 1. Introduction and Overview of Electrode Processes
does not exist. Even though the open-circuit potential of the cell is not available from
thermodynamic data, we can place it within a potential range, as shown below.
Let us now consider what occurs when a power supply (e.g., a battery) and a mi-
croammeter are connected across the cell, and the potential of the Pt electrode is made
more negative with respect to the Ag/AgBr reference electrode. The first electrode reac-
tion that occurs at the Pt is the reduction of protons,
+
2H + 2 e - * H 2 (1.1.7)
The direction of electron flow is from the electrode to protons in solution, as in Figure
1.12a, so a reduction (cathodic) current flows. In the convention used in this book, ca-
3
thodic currents are taken as positive, and negative potentials are plotted to the right. As
shown in Figure 1.1.4, the onset of current flow occurs when the potential of the Pt elec-
+
trode is near E° for the H /H 2 reaction (0 V vs. NHE or -0.07 V vs. the Ag/AgBr elec-
trode). While this is occurring, the reaction at the Ag/AgBr (which we consider the
reference electrode) is the oxidation of Ag in the presence of Br~ in solution to form
AgBr. The concentration of Br~ in the solution near the electrode surface is not changed
appreciably with respect to the original concentration (1 M), therefore the potential of the
Ag/AgBr electrode will be almost the same as at open circuit. The conservation of charge
requires that the rate of oxidation at the Ag electrode be equal to the rate of reduction at
the Pt electrode.
When the potential of the Pt electrode is made sufficiently positive with respect to the
reference electrode, electrons cross from the solution phase into the electrode, and the ox-
Pt/H+, ВГ(1 M)/AgBr/Ag Cathodic
1 : /
Onset of H +
reduction on Pt.
1 I i
\
\y
1
1.5 0 -0.5
L
/ \
1 \
/ Onset of Br"
/ oxidation on Pt
Cell Potential Anodic
Figure 1.1.4 Schematic current-potential curve for the cell Pt/H + , Br~(l M)/AgBr/Ag, showing
the limiting proton reduction and bromide oxidation processes. The cell potential is given for the Pt
electrode with respect to the Ag electrode, so it is equivalent to £ P t (V vs. AgBr). Since Âg/AgBr =
0.07 V vs. NHE, the potential axis could be converted to EPt (V vs. NHE) by adding 0.07 V to each
value of potential.
3
The convention of taking / positive for a cathodic current stems from the early polarograhic studies, where
reduction reactions were usually studied. This convention has continued among many analytical chemists and
electrochemists, even though oxidation reactions are now studied with equal frequency. Other
electrochemists prefer to take an anodic current as positive. When looking over a derivation in the literature
or examining a published i-E curve, it is important to decide, first, which convention is being used (i.e.,
"Which way is up?").
1.1 Introduction 7
idation of Br~ to Br2 (and Br^~) occurs. An oxidation current, or anodic current, flows at
potentials near the E° of the half-reaction,
Br2 + 2 e ^ 2 B r ~ (1.1.8)
which is +1.09 V vs. NHE or +1.02 V vs. Ag/AgBr. While this reaction occurs (right-
to-left) at the Pt electrode, AgBr in the reference electrode is reduced to Ag and Br~ is
liberated into solution. Again, because the composition of the Ag/AgBr/Br~ interface
(i.e., the activities of AgBr, Ag, and Br~) is almost unchanged with the passage of modest
currents, the potential of the reference electrode is essentially constant. Indeed, the essen-
tial characteristic of a reference electrode is that its potential remains practically constant
with the passage of small currents. When a potential is applied between Pt and Ag/AgBr,
nearly all of the potential change occurs at the Pt/solution interface.
The background limits are the potentials where the cathodic and anodic currents start
to flow at a working electrode when it is immersed in a solution containing only an elec-
trolyte added to decrease the solution resistance (a supporting electrolyte). Moving the
potential to more extreme values than the background limits (i.e., more negative than the
limit for H2 evolution or more positive than that for Br2 generation in the example above)
simply causes the current to increase sharply with no additional electrode reactions, be-
cause the reactants are present at high concentrations. This discussion implies that one can
often estimate the background limits of a given electrode-solution interface by consider-
ing the thermodynamics of the system (i.e., the standard potentials of the appropriate half-
reactions). This is frequently, but not always, true, as we shall see in the next example.
From Figure 1.1.4, one can see that the open-circuit potential is not well defined in
the system under discussion. One can say only that the open-circuit potential lies some-
where between the background limits. The value found experimentally will depend
upon trace impurities in the solution (e.g., oxygen) and the previous history of the Pt
electrode.
Let us now consider the same cell, but with the Pt replaced with a mercury electrode:
Hg/H + ,Br-(l M)/AgBr/Ag (1.1.9)
We still cannot calculate an open-circuit potential for the cell, because we cannot define a
redox couple for the Hg electrode. In examining the behavior of this cell with an applied
external potential, we find that the electrode reactions and the observed current-potential
behavior are very different from the earlier case. When the potential of the Hg is made
negative, there is essentially no current flow in the region where thermodynamics predict
that H2 evolution should occur. Indeed, the potential must be brought to considerably
more negative values, as shown in Figure 1.1.5, before this reaction takes place. The ther-
modynamics have not changed, since the equilibrium potential of half-reaction 1.1.7 is in-
dependent of the metal electrode (see Section 2.2.4). However, when mercury serves as
the locale for the hydrogen evolution reaction, the rate (characterized by a heterogeneous
rate constant) is much lower than at Pt. Under these circumstances, the reaction does not
occur at values one would predict from thermodynamics. Instead considerably higher
electron energies (more negative potentials) must be applied to make the reaction occur at
a measurable rate. The rate constant for a heterogeneous electron-transfer reaction is a
function of applied potential, unlike one for a homogeneous reaction, which is a constant
at a given temperature. The additional potential (beyond the thermodynamic requirement)
needed to drive a reaction at a certain rate is called the overpotential. Thus, it is said that
mercury shows "a high overpotential for the hydrogen evolution reaction."
When the mercury is brought to more positive values, the anodic reaction and the po-
tential for current flow also differ from those observed when Pt is used as the electrode.
Hg/I-Г, ВГ(1 M)/AgBr/Ag

Cathodic
Onset of H +
reduction ,
0.5 -0.5 -1.5

Onset of Hg
oxidation
Anodic
Potential (V vs. NHE)
Figure 1.1.5 Schematic current-potential curve for the Hg electrode in the cell Hg/H + , Br (1
M)/AgBr/Ag, showing the limiting processes: proton reduction with a large negative overpotential
and mercury oxidation. The potential axis is defined through the process outlined in the caption to
Figure 1.1.4.
With Hg, the anodic background limit occurs when Hg is oxidized to Hg2Br2 at a poten-
tial near 0.14 V vs. NHE (0.07 V vs. Ag/AgBr), characteristic of the half-reaction
Hg 2 Br 2 + 2e«±2Hg 2Br" (1.1.10)
In general, the background limits depend upon both the electrode material and the solu-
tion employed in the electrochemical cell.
Finally let us consider the same cell with the addition of a small amount of Cd 2 + to
the solution,
Hg/H + ,Br"(l M), Cd 2+ (10" 3 M)/AgBr/Ag (1.1.11)
The qualitative current-potential curve for this cell is shown in Figure 1.1.6. Note the
appearance of the reduction wave at about -0.4 V vs. NHE arising from the reduction
reaction
CdBr|~ + 2e S Cd(Hg) + 4Br~ (1.1.12)
where Cd(Hg) denotes cadmium amalgam. The shape and size of such waves will be cov-
ered in Section 1.4.2. If Cd 2 + were added to the cell in Figure 1.1.3 and a current-poten-
tial curve taken, it would resemble that in Figure 1.1.4, found in the absence of Cd 2 + . At a
Pt electrode, proton reduction occurs at less positive potentials than are required for the
reduction of Cd(II), so the cathodic background limit occurs in 1 M HBr before the cad-
mium reduction wave can be seen.
In general, when the potential of an electrode is moved from its open-circuit value to-
ward more negative potentials, the substance that will be reduced first (assuming all possi-
ble electrode reactions are rapid) is the oxidant in the couple with the least negative (or
most positive) E®. For example, for a platinum electrode immersed in an aqueous solution
containing 0.01 M each of F e 3 + , Sn 4 + , and N i 2 + in 1 M HC1, the first substance reduced
will be F e 3 + , since the E° of this couple is most positive (Figure 1.1.7a). When the poten-
1.1 Introduction
Hg/I-Г, ВГ(1 М), Cd2+(1mM)/AgBr/Ag
Cathodic
Onset of Cd 2 '
reduction
Anodic l _
Potential (V vs. NHE)
Figure 1.1.6 Schematic current-potential curve for the Hg electrode in the cell Hg/H+,
Br"(l M),Cd 2 + (l(T 3 M)/AgBr/Ag, showing reduction wave for Cd 2 + .
tial of the electrode is moved from its zero-current value toward more positive potentials,
the substance that will be oxidized first is the reductant in the couple of least positive (or
most negative) E°. Thus, for a gold electrode in an aqueous solution containing 0.01 M
each of Sn 2 + and F e 2 + in 1 M HI, the Sn 2 + will be first oxidized, since the E° of this cou-
ple is least positive (Figure 1.1.7b). On the other hand, one must remember that these pre-
dictions are based on thermodynamic considerations (i.e., reaction energetics), and slow
kinetics might prevent a reaction from occurring at a significant rate in a potential region
where the E° would suggest the reaction was possible. Thus, for a mercury electrode im-
mersed in a solution of 0.01 M each of Cr 3 + and Zn 2 + , in 1 M HC1, the first reduction
process predicted is the evolution of H 2 from H + (Figure 1.1.7c). As discussed earlier,
this reaction is very slow on mercury, so the first process actually observed is the reduc-
3+
tion of Cr .
1.1.2 Faradaic and Nonfaradaic Processes

Two types of processes occur at electrodes. One kind comprises reactions like those just
discussed, in which charges (e.g., electrons) are transferred across the metal-solution in-
terface. Electron transfer causes oxidation or reduction to occur. Since such reactions are
governed by Faraday's law (i.e., the amount of chemical reaction caused by the flow of
current is proportional to the amount of electricity passed), they are called faradaic
processes. Electrodes at which faradaic processes occur are sometimes called charge-
transfer electrodes. Under some conditions, a given electrode-solution interface will
show a range of potentials where no charge-transfer reactions occur because such reac-
tions are thermodynamically or kinetically unfavorable (e.g., the region in Figure 1.1.5
between 0 and —0.8 V vs. NHE). However, processes such as adsorption and desorption
can occur, and the structure of the electrode-solution interface can change with changing
potential or solution composition. These processes are called nonfaradaic processes. Al-
though charge does not cross the interface, external currents can flow (at least transiently)
when the potential, electrode area, or solution composition changes. Both faradaic and
0 Possible
reduction
Possible
oxidation 0
reactions reactions
E°
(V vs. NHE) (V w. NHE)
-0.25 N i 2 + + 2e -> Ni
Approximate
0 2 H + + 2e - » H 9 potential for -- 0
zero current (Au)
+0.15 S n 4 + + 2e -> S n 2 +
- - +0.15
\2 + 2e<-2£ +0.54
3+ + e <- F e 2 + +0.77
(Pt)-
Approximate potential
© for zero current
(a) +1.23
A u 3 + + 3e <- Au - - +1.50
0
0
-0.76 - -
-0.41 - -
0 -- (Kineticallyslow)
(Hg)
Approximate potential
for zero current
E°
(V vs. NHE)
©
(c)
Figure 1.1.7 (a) Potentials for possible reductions at a platinum electrode, initially at ~ 1 V vs.
NHE in a solution of 0.01 M each of Fe 3 + , Sn 4+ , and Ni 2+ in 1 M HCL (b) Potentials for possible
oxidation reactions at a gold electrode, initially at ~0.1V vs. NHE in a solution of 0.01 M each of
Sn 2+ and Fe 2+ in 1 M HI. (c) Potentials for possible reductions at a mercury electrode in 0.01 M
Cr 3+ and Zn 2+ in 1 M HCL The arrows indicate the directions of potential change discussed in the
text.
nonfaradaic processes occur when electrode reactions take place. Although the faradaic
processes are usually of primary interest in the investigation of an electrode reaction (ex-
cept in studies of the nature of the electrode-solution interface itself), the effects of the
nonfaradaic processes must be taken into account in using electrochemical data to obtain
information about the charge transfer and associated reactions. Consequently, we next
proceed by discussing the simpler case of a system where only nonfaradaic processes
occur.
1.2 Nonfaradaic Processes and the Nature of the Electrode-Solution Interface 11
1.2 NONFARADAIC PROCESSES AND THE NATURE OF THE

ELECTRODE-SOLUTION INTERFACE
1.2.1 The Ideal Polarized Electrode
An electrode at which no charge transfer can occur across the metal-solution interface, re-
gardless of the potential imposed by an outside source of voltage, is called an ideal polar-
ized (or ideal polarizable) electrode (IPE). While no real electrode can behave as an IPE
over the whole potential range available in a solution, some electrode-solution systems
can approach ideal polarizability over limited potential ranges,. For example, a mercury
electrode in contact with a deaerated potassium chloride solution approaches the behavior
of an IPE over a potential range about 2 V wide. At sufficiently positive potentials, the
mercury can oxidize in a charge-transfer reaction:
Hg + С Г -> |Hg 2 Cl 2 + e (at ~ +0.25 V vs. NHE) (1.2.1)

+
and at very negative potentials K can be reduced:
, Hg
K + + e -> K(Hg) (at ~ -2.1 V vs. NHE) (1.2.2)
In the potential range between these processes, charge-transfer reactions are not signifi-
cant. The reduction of water:
H 2 O + e -> | H 2 + OH" (1.2.3)
is thermodynamically possible, but occurs at a very low rate at a mercury surface unless
quite negative potentials are reached. Thus, the only faradaic current that flows in this re-
gion is due to charge-transfer reactions of trace impurities (e.g., metal ions, oxygen, and
organic species), and this current is quite small in clean systems. Another electrode that
behaves as an IPE is a gold surface hosting an adsorbed self-assembled monolayer of
alkane thiol (see Section 14.5.2).
1.2.2 Capacitance and Charge of an Electrode

Since charge cannot cross the IPE interface when the potential across it is changed, the
behavior of the electrode-solution interface is analogous to that of a capacitor. A capaci-
tor is an electrical circuit element composed of two metal sheets separated by a dielectric
material (Figure 1.2.1a). Its behavior is governed by the equation
| =С (1.2.4)
e ^-
e
Battery — _ Capacitor
++ ++
©
e
Figure 1.2.1 (a) A capacitor, (b)
(b) Charging a capacitor with a battery.
Metal Solution Metal Solution
Figure 1.2.2 The metal-solution

interface as a capacitor with a
charge on the metal, qM, (a)
(a) (b) negative and (b) positive.
where q is the charge stored on the capacitor (in coulombs, С), Е is the potential across the
capacitor (in volts, V), and С is the capacitance (in farads, F). When a potential is applied
across a capacitor, charge will accumulate on its metal plates until q satisfies equation
1.2.4. During this charging process, a current (called the charging current) will flow. The
charge on the capacitor consists of an excess of electrons on one plate and a deficiency of
electrons on the other (Figure 1.2.1b). For example, if a 2-V battery is placed across a 10-
/л¥ capacitor, current will flow until 20 /лС has accumulated on the capacitor plates. The
magnitude of the current depends on the resistance in the circuit (see also Section 1.2.4).
The electrode-solution interface has been shown experimentally to behave like a ca-
pacitor, and a model of the interfacial region somewhat resembling a capacitor can be
given. At a given potential, there will exist a charge on the metal electrode, qM, and a
charge in the solution, qs (Figure 1.2.2). Whether the charge on the metal is negative or
positive with respect to the solution depends on the potential across the interface and the
composition of the solution. At all times, however, qM — -qs. (In an actual experimental
arrangement, two metal electrodes, and thus two interfaces, would have to be considered;
we concentrate our attention here on one of these and ignore what happens at the other.)
The charge on the metal, qM, represents an excess or deficiency of electrons and resides in
a very thin layer (<0.1 A) on the metal surface. The charge in solution, qs, is made up of
an excess of either cations or anions in the vicinity of the electrode surface. The charges
qM and qs are often divided by the electrode area and expressed as charge densities, such
as, ( j M = qM/A, usually given in /лС/ст2. The whole array of charged species and ori-
ented dipoles existing at the metal-solution interface is called the electrical double layer
(although its structure only very loosely resembles two charged layers, as we will see in
Section 1.2.3). At a given potential, the electrode- solution interface is characterized by a
double-layer capacitance, C<j, typically in the range of 10 to 40 /^F/cm2. However, unlike
real capacitors, whose capacitances are independent of the voltage across them, Q is
often a function of potential.4
1.2.3 Brief Description of the Electrical Double Layer

The solution side of the double layer is thought to be made up of several "layers." That
closest to the electrode, the inner layer, contains solvent molecules and sometimes other
species (ions or molecules) that are said to be specifically adsorbed (Figure 1.2.3). This
inner layer is also called the compact, Helmholtz, or Stern layer. The locus of the electri-
4
In various equations in the literature and in this book, Cj may express the capacitance per unit area and be
given in fxF/cm2, or it may express the capacitance of a whole interface and be given in JJLF. The usage for a
given situation is always apparent from the context or from a dimensional analysis.
:
IHP OHP
ф1 ф2
Diffuse layer
Solvated cation
Metal
Specifically adsorbed anion
= Solvent molecule
Figure 1.2.3 Proposed model of the
double-layer region under conditions
where anions are specifically adsorbed.
cal centers of the specifically adsorbed ions is called the inner Helmholtz plane (IHP),
which is at a distance x\. The total charge density from specifically adsorbed ions in this
inner layer is а1 (/лС/ст2). Solvated ions can approach the metal only to a distance x2; the
locus of centers of these nearest solvated ions is called the outer Helmholtz plane (OHP).
The interaction of the solvated ions with the charged metal involves only long-range elec-
trostatic forces, so that their interaction is essentially independent of the chemical proper-
ties of the ions. These ions are said to be nonspecifically adsorbed. Because of thermal
agitation in the solution, the nonspecifically adsorbed ions are distributed in a three-
dimensional region called the dijfuse layer, which extends from the OHP into the bulk of
the solution. The excess charge density in the diffuse layer is <7d, hence the total excess
charge density on the solution side of the double layer, cr s , is given by
= _ом (1.2.5)
The thickness of the diffuse layer depends on the total ionic concentration in the solution;
for concentrations greater than 10~2 M, the thickness is less than ~100 A. The potential
profile across the double-layer region is shown in Figure 1.2.4.
The structure of the double layer can affect the rates of electrode processes. Consider
an electroactive species that is not specifically adsorbed. This species can approach the
electrode only to the OHP, and the total potential it experiences is less than the potential
between the electrode and the solution by an amount ф2 — </>s, which is the potential drop
across the diffuse layer. For example, in 0.1 M NaF, ф2 — <£s is —0.021 V at E = -0.55
V vs. SCE, but it has somewhat larger magnitudes at more negative and more positive po-
tentials. Sometimes one can neglect double-layer effects in considering electrode reaction
kinetics. At other times they must be taken into account. The importance of adsorption
and double-layer structure is considered in greater detail in Chapter 13.
One usually cannot neglect the existence of the double-layer capacitance or the pres-
ence of a charging current in electrochemical experiments. Indeed, during electrode reac-
tions involving very low concentrations of electroactive species, the charging current can
be much larger than the faradaic current for the reduction or oxidation reaction. For this
reason, we will briefly examine the nature of the charging current at an IPE for several
types of electrochemical experiments.
- Metal — > Ц Solution >-

N
'I i (+) Solvated cation
0
!©
ч
)\ j ~' "Ghost" of anion repelled
from electrode surface
ф2
Figure 1.2.4 Potential profile across the
double-layer region in the absence of specific
adsorption of ions. The variable ф, called the
inner potential, is discussed in detail in
Section 2.2. A more quantitative
representation of this profile is shown in
x2
Figure 12.3.6.
1.2.4 Double-Layer Capacitance and Charging

Current in Electrochemical Measurements
Consider a cell consisting of an IPE and an ideal reversible electrode. We can approxi-
mate such a system with a mercury electrode in a potassium chloride solution that is also
in contact with an SCE. This cell, represented by Hg/K+, CF/SCE, can be approximated
by an electrical circuit with a resistor, Rs, representing the solution resistance and a capac-
itor, C(j, representing the double layer at the Hg/K+,C1~ interface (Figure 1.2.5).5 Since
нд
drop
electrode
HI Wv II
-AM о
SCE
Figure 1.2.5 Left: Two-electrode cell with an ideal polarized mercury drop electrode and an SCE.
Right: Representation of the cell in terms of linear circuit elements.
Actually, the capacitance of the SCE, С$СЕ, should also be included. However, the series capacitance of C d and
CSCE is C T = CdCSCEJ[Cd + CSCEL and normally C S C E » Q> so that C T « C d . Thus, C S C E can be neglected
in the circuit.
1.2 Nonfaradaic Processes and the Nature of the Electrode-Solution Interface «I 15
Cd is generally a function of potential, the proposed model in terms of circuit elements is

strictly accurate only for experiments where the overall cell potential does not change
very much. Where it does, approximate results can be obtained using an "average" Cd
over the potential range.
Information about an electrochemical system is often gained by applying an electrical
perturbation to the system and observing the resulting changes in the characteristics of the
system. In later sections of this chapter and later chapters of this book, we will encounter
such experiments over and over. It is worthwhile now to consider the response of the IPE
system, represented by the circuit elements Rs and Q in series, to several common electri-
cal perturbations.
(a) Voltage (or Potential) Step

The result of a potential step to the IPE is the familiar RC circuit problem (Figure
1.2.6). The behavior of the current, /, with time, t, when applying a potential step of
magnitude E, is
(1.2.6)
R
This equation is derived from the general equation for the charge, q, on a capacitor as
a function of the voltage across it, EQ\
q = CdEc (1.2.7)
At any time the sum of the voltages, £ R and EQ, across the resistor and the capacitor, re-
spectively, must equal the applied voltage; hence
E= Er = iR* + 4- (1.2.8)
Noting that / = dq/dt and rearranging yields

dq -q
(1.2.9)
dt RsCd Rs
If we assume that the capacitor is initially uncharged (q = 0 at t = 0), then the solution of
(1.2.9) is
q = ECd[l - e~t/RsCd] (1.2.10)
By differentiating (1.2.10), one obtains (1.2.6). Hence, for a potential step input, there is
an exponentially decaying current having a time constant, т = RsCd (Figure 1.2.7). The
current for charging the double-layer capacitance drops to 37% of its initial value at t = т,
and to 5% of its initial value at t = 3r. For example, if Rs = 1 ft and Cd = 20 fxF, then
т = 20 /JLS and double-layer charging is 95% complete in 60 /xs.
Figure 1.2.6 Potential step experiment for an RC

circuit.
16 P Chapter 1. Introduction and Overview of Electrode Processes
Resultant (/)
• Applied
(E)
Figure 1.2.7 Current

transient (/ vs. t) resulting from
a potential step experiment.
(b) Current Step

When the RsCd circuit is charged by a constant current (Figure 1.2.8), then equation 1.2.8
again applies. Since q = Jidt, and / is a constant,
E = iRK + 4r\ dt (1.2.11)
or
E = i(Rs + t/Cd) (1.2.12)
Hence, the potential increases linearly with time for a current step (Figure 1.2.9).
(c) Voltage Ramp (or Potential Sweep)

A voltage ramp or linear potential sweep is a potential that increases linearly with time
starting at some initial value (here assumed to be zero) at a sweep rate и (in V s" 1 ) (see
Figure 1.2.10a).
E = vt (1.2.13)
Figure 1.2.8 Current step experiment for an RC

Constant current source circuit.
-Slope = i - Resultants
• Applied
(0
_ Figure 1.2.9 E-t behavior resulting

t from a current step experiment.
If such a ramp is applied to the RSC^ circuit, equation 1.2.8 still applies; hence
vt = Rs(dq/dt) + q/Cd (1.2.14)
lfq = OaU = 0,
(1.2.15)
The current rises from zero as the scan starts and attains a steady-state value, vCd (Figure
1.2.10b). This steady-state current can then be used to estimate Cd. If the time constant,
Applied E(t)
(a)
Resultant i
Figure 1.2.10 Current-time

behavior resulting from a linear
potential sweep applied to an RC
(b) circuit.
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by the Mediterranean race. They occur in great numbers, size and variety along the north coast of
Africa and up the Atlantic seaboard through Spain, Brittany and England to Scandinavia.
It is admitted that the various groups of the Mediterranean race did not speak in the first instance
any form of Aryan tongue and we know that these languages were introduced into the Mediterranean
world by invaders from the north.
In Spain the language of the Nordic invaders was Celtic and is believed to have nearly died out by
Roman times. Its remnants and the ancient speech of the natives were in turn superseded, along with
the Phœnician spoken in some of the southern coast towns, by the Latin of the conquering Roman.
Latin mixed with some small elements of Gothic construction and Arabic vocabulary forms to-day the
basis of modern Portuguese, Castilian and Catalan.
The native Mediterranean race of the Iberian Peninsula quickly absorbed the blood of these Celtic-
speaking Nordic Gauls, just as it later diluted beyond recognition the vigorous physical characters of
the Nordic Vandals, Suevi and Visigoths. A certain amount of Nordic blood still persists to-day in
northern Spain, especially in Galicia and along the Pyrenees, as well as generally among the upper
classes. According to classic writers there were light and dark types in Spain in Roman times. The
Romans left no evidence of their domination except in their language and religion; while the earlier
Phœnicians on the coasts and the later swarms of Moors and Arabs all over the peninsula, but chiefly
in the south, were closely related by race to the native Iberians.
That portion of the Mediterranean race which inhabits southern France occupies most of the
territory of ancient Languedoc and Provence and it was these Provençals who developed and preserved
during the Middle Ages the romantic civilization of the Albigensians, a survival of classic culture which
was drowned in blood by a crusade from the north in the thirteenth century.
In northern Italy only the coast of Liguria is occupied by the Mediterranean race. In the valley of the
Po the Mediterraneans predominated during the early Neolithic but with the introduction of bronze
the Alpines appear and round skulls to this day prevail north of the Apennines. About 1100 B. C. the
Nordic Umbrians and Oscans swept over the Alps from the northeast, conquered northern Italy and
introduced their Aryan speech, which gradually spread southward. The Umbrian state was afterward
overwhelmed by the Tyrrhenians or Etruscans, who were of Mediterranean race and who, by 800 B. C.
had extended their empire northward to the Alps and temporarily checked the advance of the Nordics.
In the sixth century B. C. new swarms of Nordics, coming this time from Gaul and speaking Celtic
dialects, seized the valley of the Po and in 382 B. C. these Gauls, heavily reinforced from the north and
under the leadership of Brennus, stormed Rome and completely destroyed the Etruscan power. From
that time onward the valley of the Po became known as Cisalpine Gaul. Mixed with other Nordic
elements, chiefly Gothic and Lombard, this population persists to this day, and is the backbone of
modern Italy.
A continuation of this movement of these Gauls, or Galatians as the Greek world called them,
starting from northern Italy occurred a century later when these Nordics suddenly appeared before
Delphi in Greece in 279 B. C. and then crossed into Asia Minor and founded the state called Galatia,
which endured until Christian times.
South Italy until its conquest by Rome was Magna Græcia and the population to-day retains many
Pelasgian Greek elements. It is among these classic remnants that artists search for the handsomest
specimens of the Mediterranean race. In Sicily also the race is purely Mediterranean in spite of the
admixture of types coming from the neighboring coasts of Tunis. These intrusive elements, however,
were all of kindred race. Traces of Alpines in these regions and on the adjoining African coast are very
scarce and wherever found may be referred to the final wave of round skull invasion which introduced
bronze into Europe.
In Greece the Mediterranean Pelasgians speaking a Non-Aryan tongue were conquered by the
Nordic Achæans, who entered from the northeast according to tradition prior to 1250 B. C. probably
between 1400 and 1300 B. C. Doubtless there were still earlier waves of these same Nordic invaders as
far back as 1700 B. C., which was a period of general unrest and migration throughout the ancient
world.
The Nordic Achæans and Mediterranean Pelasgians as yet unmixed stand out in clear contrast in the
Homeric account of the ten year siege of Troy, which is generally assigned to the date of 1194 to 1184 B.
C.
The same invasion that brought the Achæans into Greece brought a related Nordic people to the
coast of Asia Minor, known as Phrygians. Of this race were the Trojan leaders.
Both the Trojans and the Greeks were commanded by huge blond princes, the heroes of Homer—in
fact, even the Gods were fair-haired—while the bulk of the armies on both sides was composed of little
brunet Pelasgians, imperfectly armed and remorselessly butchered by the leaders on either side. The
only common soldiers mentioned by Homer as of the same race as the heroes were the Myrmidons of
Achilles.
About the time that the Achæans and the Pelasgians began to amalgamate, new hordes of Nordic
barbarians collectively called Hellenes entered from the northern mountains and destroyed this old
Homeric-Mycenæan civilization. This Dorian invasion took place a little before 1100 B. C. and brought
in the three main Nordic strains of Greece, the Dorian, the Æolian and the Ionian groups, which
remain more or less distinct and separate throughout Greek history. Among these Nordics the Dorians
may have included some Alpine elements. It is more than probable that this invasion or swarming of
Nordics into Greece was part of the same general racial upheaval that brought the Umbrians and
Oscans into Italy.
Long years of intense and bitter conflict follow between the old population and the newcomers and
when the turmoil of this revolution settled down classic Greece appears. What was left of the Achæans
retired to the northern Peloponnesus and the survivors of the early Pelasgian population remained in
Messenia serving as helots their Spartan masters. The Greek colonies in Asia Minor were founded
largely by refugees fleeing from these Dorian invaders.
The Pelasgian strain seems to have persisted best in Attica and the Ionian states. The Dorian
Spartans appear to have retained more of the character of the northern barbarians than the Ionian
Greeks but the splendid civilization of Hellas was due to a fusion of the two elements, the Achæan and
Hellene of Nordic and the Pelasgian of Mediterranean race.
The contrast between Dorian Sparta and Ionian Athens, between the military efficiency, thorough
organization and sacrifice of the citizen for the welfare of the state, which constituted the basis of
Lacedæmonian power, and the Attic brilliancy, instability and extreme development of individualism,
is strikingly like the contrast between Prussia with its Spartan-like culture and France with its
Athenian versatility.
To this mixture of races in classic Greece the Mediterranean Pelasgians contributed their Mycenæan
culture and the Nordic Achæans and Hellenes contributed their Aryan language, fighting efficiency and
the European aspect of Greek life.
The first result of a crossing of two such contrasted subspecies as the Nordic and Mediterranean
races has repeatedly been a new outburst of civilization. This occurs as soon as the older race has
imparted to the conquerors its culture and before the victors have allowed their blood to be attenuated
by mixture. This process seems to have happened several times in Greece.
Later, in 338 B. C., when the original Nordic blood had been hopelessly diluted by mixture with the
ancient Mediterranean elements, Hellas fell an easy prey to Macedon. The troops of Philip and
Alexander were Nordic and represented the uncultured but unmixed ancestral type of the Achæans and
Hellenes. Their unimpaired fighting strength was irresistible as soon as it was organized into the
Macedonian phalanx, whether directed against their degenerate brother Greeks or against the
Persians, whose original Nordic elements had also by this time practically disappeared. When in its
turn the pure Macedonian blood was impaired by intermixture with Asiatics, they, too, vanished and
even the royal Macedonian dynasties in Asia and Egypt soon ceased to be Nordic or Greek except in
language and customs.
It is interesting to note that the Greek states in which the Nordic element most predominated
outlived the other states. Athens fell before Sparta and Thebes outlived them both. Macedon in classic
times was considered quite the most barbarous state in Hellas and was scarcely recognized as forming
part of Greece, but it was through the military power of its armies and the genius of Alexander that the
Levant and western Asia became Hellenized. Alexander with his Nordic features, aquiline nose, fair
skin, gently curling light hair and mixed eyes, the left blue and the right very black, typifies this Nordic
conquest of the Near East.
It is scarcely possible to-day to find in purity the physical traits of the ancient race in the Greek-
speaking lands and islands and it is chiefly among the pure Nordics of Anglo-Norman type that there
occur those smooth and regular classic features, especially the brow and nose lines, that were the
delight of the sculptors of Hellas.
To what extent any of the blood of the ancient Hellenes flows in the veins of the Greeks of to-day is
difficult to determine but it should be found, if anywhere, in Crete and in the Ægean Islands. The
modern Greek is trying to purify his language back to classic Ionian and to appropriate the traditions of
the mighty Past, but to do this something more is needed than the naming of children after
Agamemnon and Hecuba. Even in Roman times, the ancient Greek of the classic period was little more
than a tradition and the term Græculus given to the contemporary Hellenes was one of contempt.
Concerning the physical type of classic in contrast to Homeric Greece, we know that the Greeks were
predominantly long-headed and of relatively short stature in comparison with the northern barbarians.
The modern Greeks are also relatively short in stature, but are moderately round-headed. As to color
these modern Greeks are substantially all dark as to eye and hair, with a somewhat swarthy skin.
Among Albanians and such Greeks as show blond traits light eyes are more than ten times as
numerous as light hair. The Albanians are members of the tall, round-headed Dinaric race and have
distant relationship with the Nordics. They may possibly represent an ancient cross between Nordics
and Alpines and they constitute to-day a marked subdivision of the latter. They resemble the Round
Barrow brachycephs who entered Britain just before or at the opening of the Bronze Age and who are
still scantily represented among the living English and Welsh. This type called the Beaker Maker or
Borreby type is characterized by a moderately round head and great stature, strength and considerable
intellectual force. The Albanian or Dinaric type was not, so far as we know, represented in ancient
Greece although some modern archæologists have suggested that the Spartans were of this type. We
have as yet no evidence of the color, size and skull shape of the Spartans, but we do know that their
Dorian ancestors claimed to have come from or through the mountains of northern Epirus (Albania).
The Dorian dialects are also said to be more closely related to modern Albanian—which is derived from
the ancient Illyrian—than are the Ionian dialects. The Spartan character, if that be any test of race, was
heavy, slow and steady, and would indicate northern rather than Mediterranean antecedents.
Concerning modern Europe north of the Alps, culture came from the south and not from the east
and to the Mediterranean subspecies is due the foundation of our civilization. The ancient
Mediterranean world was for the most part of this race; the long-sustained civilization of Egypt, which
endured for thousands of years in almost uninterrupted sequence; the brilliant Minoan Empire of
Crete, which flourished between 3000 and 1200 B. C. and was the ancestor of the Mycenæan cultures
of Greece, Cyprus, Italy and Sardinia; the mysterious Empire of Etruria, the predecessor and teacher of
Rome; the Hellenic states and colonies throughout the Mediterranean and Black Seas; the maritime
and mercantile power of Phœnicia and its mighty colony, imperial Carthage; all were the creation of
this race. The sea empire of Crete, when its royal palace at Cnossos was burned by the ‘sea peoples’ of
the north, passed to Tyre, Sidon and Carthage and from them to the Greeks. The early development of
the art of navigation is to be attributed to this race and from them the North centuries later learned its
maritime architecture.
Even though the Mediterranean race has no claim to the invention of the synthetic languages and
though it played a relatively small part in the development of the civilization of the Middle Ages or of
modern times, nevertheless to it belongs the chief credit of the classic civilization of Europe in the
sciences, art, poetry, literature and philosophy, as well as the major part of the civilization of Greece
and a very large share in the Empire of Rome.
In the Eastern Empire the Mediterraneans were the predominant factor under the guise of Byzantine
Greeks. Owing to the fact that our histories have been written under the influence of Roman orthodoxy
and because in the eyes of the Frankish Crusaders the Byzantine Greeks were heretics, they have been
regarded by us as degenerate cowards.
But throughout the Middle Ages Byzantium represented in unbroken sequence the Empire of Rome
in the East and as the capital of that Empire it held Mohammedan Asia in check for nearly a thousand
years. When at last in 1453 the imperial city deserted by western Christendom was stormed by the
Ottoman Turks and Constantine, last of Roman Emperors, fell sword in hand there was enacted one of
the greatest tragedies of all time.
With the fall of Constantinople the Empire of Rome passes finally from the scene of history and the
development of civilization is transferred from Mediterranean lands and from the Mediterranean race
to the North Sea and to the Nordic race.
VI
THE NORDIC RACE
We have shown that the Mediterranean race entered Europe from the south and forms part of a
great group of peoples extending into southern Asia, that the Alpine race came from the east through
Asia Minor and the valley of the Danube and that its present European distribution is merely the
westernmost point of an ethnic pyramid, the base of which rests solidly on the round skulled peoples of
the great plateaux of central Asia. Both of these races are, therefore, western extensions of Asiatic
subspecies and neither of them can be considered as exclusively European.
With the remaining race, the Nordic, however, the case is different. This is a purely European type,
in the sense that it has developed its physical characters and its civilization within the confines of that
continent. It is, therefore, the Homo europæus, the white man par excellence. It is everywhere
characterized by certain unique specializations, namely, wavy brown or blond hair and blue, gray or
light brown eyes, fair skin, high, narrow and straight nose, which are associated with great stature and
a long skull, as well as with abundant head and body hair.
A composite picture of this Nordic race and remarkable examples of its best contemporary types can
be found in the English illustrated weeklies, which are publishing during this great war the lists and
portraits of their officers who have fallen in battle. No nation, not even England although richly
endowed with a Nordic gentry, can stand the loss of so much good blood. Here is the evidence, if such
be needed, of the actual Passing of the Great Race.
Abundance of hair is an ancient and generalized character which the Nordics share with the Alpines
of both Europe and Asia, but the light colored eyes and light colored hair are characters of relatively
recent specialization and consequently highly unstable.
The pure Nordic race is at present clustered around the shores of the Baltic and North Seas from
which it has spread west and south and east fading off gradually into the two preceding races.
The centre of its greatest purity is now in Sweden and there is no doubt that at first the Scandinavian
Peninsula and later, also, the immediately adjoining shores of the Baltic were the centres of radiation
of the Teutonic or Scandinavian branch of this race.
The population of Scandinavia has been composed of this Nordic subspecies from the
commencement of Neolithic times and Sweden to-day represents one of the few countries which has
never been overwhelmed by foreign conquest and in which there has been but a single racial type from
the beginning. This nation is unique in its unity of race, language, religion and social ideals.
Southern Scandinavia only became fit for human habitation on the retreat of the glaciers about
twelve thousand years ago and apparently was immediately occupied by the Nordic race. This is one of
the few geological dates which is absolute and not relative. It rests on a most interesting series of
computations made by Baron DeGeer, based on an actual count of the laminated deposits of clay laid
down annually by the retreating glaciers, each layer representing the summer deposit of the subglacial
stream.
The Nordics first appear at the close of the Paleolithic along the coasts of the Baltic. The earliest
industry discovered in this region, named the Maglemose and found in Denmark and elsewhere
around the Baltic, is probably the culture of the Proto-Teutonic branch of the Nordic race. No human
remains in connection therewith have been found.
The vigor and power of the Nordic race as a whole is such that it could not have been evolved in so
restricted an area as southern Sweden although its Teutonic or Scandinavian section did develop there
in comparative isolation. The Nordics must have had a larger field for their specialization and a longer
period for their evolution than is afforded by the limited time which has elapsed since Sweden became
habitable. For the development of so marked a type there is required a continental area isolated and
protected for long ages from the intrusion of other races. The climatic conditions must have been such
as to impose a rigid elimination of defectives through the agency of hard winters and the necessity of
industry and foresight in providing the year’s food, clothing and shelter during the short summer. Such
demands on energy if long continued would produce a strong, virile and self-contained race which
would inevitably overwhelm in battle nations whose weaker elements had not been purged by the
conditions of an equally severe environment.
An area conforming to these requirements is offered by the forests and plains of eastern Germany,
Poland and Russia. It was here that the Proto-Nordic type evolved and here their remnants are found.
They were protected from Asia on the east by the then almost continuous water connections across
eastern Russia between the White Sea and the old Caspian-Aral Sea.
During the last glacial advance (known as the Würm) which, like the preceding glaciations, is
believed to have been a period of land depression, the White Sea extended far to the south of its
present limits, while the enlarged Caspian Sea, then and long afterward connected with the Sea of Aral,
extended northward to the great bend of the Volga. The intermediate area was studded with large lakes
and morasses. Thus an almost complete water barrier of shallow sea located just west of the low Ural
Mountains, separated Europe from Asia during the Würm glaciation and the following period of glacial
retreat. The broken connection was restored just before the dawn of history by a slight elevation of the
land and the shrinking of the Caspian-Aral Sea through the increasing desiccation which has left its
present surface below sea level.
An important element in the maintenance of the isolation of this Nordic cradle on the south is the
fact that from earliest times down to this day the pressure of population has been unchangeably from
the bleak and sterile north, southward and eastward, into the sunny but enervating lands of France,
Italy, Greece, Persia and India.
In these forests and steppes of the north, the Nordic race gradually evolved in isolation and at an
early date spread north over the Scandinavian Peninsula together with much of the land now
submerged under the Baltic and North Seas.
Nordic strains form everywhere a substratum of population throughout Russia and underlie the
round skulled Slavs who first appear a little over a thousand years ago as coming not from the direction
of Asia but from south Poland. Burial mounds called kurgans are widely scattered throughout Russia
from the Carpathians to the Urals and contain numerous remains of a dolichocephalic race,—in fact,
more than three-fourths of the skulls are of this type. Round skulls first become numerous in ancient
Russian graveyards about 900 A. D. and soon increase to such an extent that in the Slavic period from
the ninth to the thirteenth centuries one-half of the skulls were brachycephalic, while in modern
cemeteries the proportion of round skulls is still greater. The ancient Nordic element, however, still
forms a very considerable portion of the population of northern Russia and contributes the blondness
and the red-headedness so characteristic of the Russian of to-day. As we leave the Baltic coasts the
Nordic characters fade out both toward the south and east. The blond element in the nobility of Russia
is of later Scandinavian and Teutonic origin.
When the seas which separated Russia from Asia dried, when the isolation and exacting climate of
the north had done their work and produced the vigorous Nordic type, and when in the fulness of time
bronze for their weapons reached them these men burst upon the southern races, conquering east,
south and west. They brought with them from the north the hardihood and vigor acquired under the
rigorous selection of a long winter season and vanquished in battle the inhabitants of older and feebler
civilizations, but only to succumb in their turn to the softening influences of a life of ease and plenty in
their new homes.
The earliest recorded appearance of Aryan-speaking Nordics is our first dim vision of the Sacæ
introducing Sanskrit into India, the Cimmerians pouring through the passes of the Caucasus from the
grasslands of South Russia to invade the Empire of the Medes and the Achæans and Phrygians
conquering Greece and the Ægean coast of Asia Minor. About 1100 B. C. Nordics enter Italy as
Umbrians and Oscans and soon after other Nordics cross the Rhine into Gaul. The latter were the
western vanguard of the Celtic-speaking tribes which had long occupied those districts in Germany
which lay south and west of the Teutonic Nordics. These Teutons at this early date were confined
probably to Scandinavia and the immediate shores of the Baltic and were just beginning to press
southward.
This first Celtic wave of Nordics seems to have swept westward along the sandy plains of northern
Europe, and entered France through the Low Countries. From this point as Goidels they spread north
into Britain, reaching there about 800 B. C. As Gauls they conquered all France and pushed on
southward and westward into Spain and over the Maritime Alps into northern Italy, where they
encountered the kindred Nordic Umbrians, who at an earlier date had crossed the Alps from the
northeast. Other Celtic-speaking Nordics apparently migrated up the Rhine and down the Danube and
by the time the Romans came on the scene the Alpines of central Europe had been thoroughly
Celticized. These tribes pushed eastward into southern Russia and reached the Crimea as early as the
fourth century B. C. Mixed with the natives, they were called by the Greeks the Celto-Scyths. This
swarming out of what is now called Germany of the first Nordics was during the closing phases of the
Bronze Period and was contemporary with and probably caused by the first great expansion of the
Teutons from Scandinavia by way both of Denmark and the Baltic coasts.
These invaders were succeeded by a second wave of Celtic-speaking peoples, the Cymry or Brythons,
who drove their Goidelic predecessors still farther westward and exterminated and absorbed them over
large areas. These Cymric invasions occurred about 300–100 B. C. and were probably the result of the
growing development of the Teutons and their final expulsion of the Celtic-speaking tribes from
Germany. These Cymry occupied northern France under the name of Belgæ and invaded England as
Brythons in several waves, the last being the true Belgæ. The conquests of these Cymric tribes in both
Gaul and Britain were only checked by the legions of Rome.
These migrations are exceedingly hard to trace because of the confusion caused by the fact that Celtic
speech is now found on the lips of populations in nowise related to the Nordics who first introduced it.
But one fact stands out clearly, all the original Celtic-speaking tribes were Nordic.
What were the special physical characters of these tribes in which they differed from their Teutonic
successors is now impossible to say, beyond the possible suggestion that in the British Isles the Scottish
and Irish populations in which red hair and gray or green eyes are abundant have rather more of this
Celtic strain in them than have the flaxen haired Teutons, whose china-blue eyes are clearly not Celtic.
When the peoples called Gauls or Celts by the Romans and Galatians by the Greeks first appear in
history they are described in exactly the same terms as were later the Teutons. They were all gigantic
barbarians with fair and very often red hair, then more frequent than to-day, with gray or fiercely blue
eyes and were thus clearly members of the Nordic subspecies.
The first Celtic-speaking nations with whom the Romans came in contact were Gaulish and had
probably incorporated much Alpine blood by the time they crossed the mountains into the domain of
classic history. The Nordic element had become still weaker by absorption from the conquered
populations when at a later date the Romans broke through the ring of Celtic nations and came into
contact with the Nordic Cymry and Teutons.
After these early expansions of Gauls and Cymry the Teutons appear upon the scene. Of the pure
Teutons within the ken of history, it is not necessary to mention more than the most important of the
long series of conquering tribes.
The greatest of them all were perhaps the Goths, who came originally from the south of Sweden and
were long located on the opposite German coast at the mouth of the Vistula. From here they crossed
Poland to the Crimea where they were known in the first century. Three hundred years later they were
driven westward by the Huns and forced into the Dacian plain and over the Danube into the Roman
Empire. There they split up; the Ostrogoths after a period of subjection to the Huns on the Danube,
ravaged the European provinces of the Eastern Empire, conquered Italy and founded there a great but
shortlived nation. The Visigoths occupied much of Gaul and then entered Spain driving the Nordic
Vandals before them into Africa. The Teutons and Cimbri, destroyed by Marius in southern Gaul about
100 B. C., the Gepidæ, the Alans, the Suevi, the Vandals, the Alemanni of the upper Rhine, the
Marcomanni, the Saxons, the Batavians, the Frisians, the Angles, the Jutes, the Lombards and the
Heruli of Italy, the Burgundians of the east of France, the Franks of the lower Rhine, the Danes, and,
latest of all, the Norse Vikings emerge from the northern forests and seas one after another and sweep
through history. Less well known but of great importance are the Varangians, who coming from
Sweden in the ninth and tenth centuries, conquered the coast of the Gulf of Finland and much of White
Russia and left there a dynasty and aristocracy of Nordic blood. In the tenth and eleventh centuries
they were the rulers of Russia.
The traditions of Goths, Vandals, Lombards and Burgundians all point to Sweden as their earliest
homeland and probably all the pure Teutonic tribes came originally from Scandinavia and were closely
related.
When these Teutonic tribes poured down from the Baltic coasts, their Celtic-speaking Nordic
predecessors were already much mixed with the underlying populations, Mediterranean in the west
and Alpine in the south. These “Celts” were not recognized by the Teutons as kin in any sense and were
all called, Welsh, or foreigners. From this word are derived the names “Wales,” “Cornwales” or
“Cornwall,” “Valais,” “Walloons,” and “Vlach” or “Wallachian.”
VII
TEUTONIC EUROPE
No proper understanding is possible of the meaning of the history of Christendom or full

appreciation of the place in it of the Teutonic Nordics without a brief review of the events in Europe of
the last two thousand years.
When Rome fell and changed trade conditions necessitated the transfer of power from its historic
capital in Italy to a strategic situation on the Bosporus, western Europe was definitely and finally
abandoned to its Teutonic invaders. These same barbarians swept up again and again to the Propontis,
only to recoil before the organized strength of the Byzantine Empire and the walls of Mikklegard. The
final line of cleavage between the western and eastern Empires corresponded closely to the boundaries
of Latin and Greek speech and differences of language no doubt were the chief cause of the political
and later of the religious divergence between them.
Until the coming of the Alpine Slavs the Eastern Empire still held in Europe the Balkan Peninsula
and much of the eastern Mediterranean. The Western Empire, however, collapsed utterly under the
impact of hordes of Nordic Teutons at a much earlier date. In the fourth and fifth centuries of our era
north Africa, once the empire of Carthage, had become the seat of the kingdom of Nordic Vandals.
Spain fell under the control of the Visigoths and Lusitania, now Portugal, under that of the Suevi. Gaul
was Visigothic in the south and Burgundian in the east, while the Frankish kingdom dominated the
north until it finally absorbed and incorporated all the territories of ancient Gaul and made it the land
of the Franks. Strictly speaking, the northern half of France and the adjoining districts, the country of
Langued’oil, is the true land of the Franks while the southern Languedoc was never Frankish except by
conquest, and was never as thoroughly Nordicized as the north. Whatever Nordic elements are still to
be found there are Gothic and Burgundian but not Frankish.
Italy fell under the control first of the Ostrogoths and then of the Lombards. The purely Nordic
Saxons with kindred tribes conquered the British Isles and meanwhile the Norse and Danish
Scandinavians contributed a large element to all the coast populations as far south as Spain and the
Swedes organized in the eastern Baltic what is now Russia.
Thus when Rome passed all Europe had become superficially Teutonic. At first these Teutons were
isolated and independent tribes bearing some shadowy relation to the one organized state they knew,
the Empire of Rome. Then came the Mohammedan invasion, which reached western Europe from
Africa and destroyed the Visigothic kingdom. The Moslems swept on unchecked until their light
horsemen dashed themselves to pieces against the heavy armed cavalry of Charles Martel and his
Franks at Tours in 732 A. D.
The destruction of the Vandal kingdom by the armies of the Byzantine Empire, the conquest of Spain
by the Moors and finally the overthrow of the Lombards by the Franks were all greatly facilitated by the
fact that these barbarians, Vandals, Goths, Suevi and Lombards, with the sole exception of the Franks,
were originally Christians of the Arian or Unitarian confession and as such were regarded as heretics
by their orthodox Christian subjects. The Franks alone were converted from heathenism directly to the
Trinitarian faith to which the old populations of the Roman Empire adhered. From this orthodoxy of
the Franks arose the close relation between France, “the eldest daughter of the church,” and the
papacy, a connection which lasted for more than a thousand years—in fact nearly to our own day.
With the Goths eliminated western Christendom became Frankish. In the year 800 A. D.
Charlemagne was crowned at Rome and re-established the Roman Empire in the west, which included
all Christendom outside of the Byzantine Empire. In some form or shape this Roman Empire endured
until the beginning of the nineteenth century and during all that time it formed the basis of the political
concept of European man.
This same concept lies to-day at the root of the imperial idea. Kaiser, Tsar and Emperor each takes
his name and in some way undertakes to trace his title from Cæsar and the Empire. Charlemagne and
his successors claimed and often exercised overlordship as to all the other continental Christian
nations and when the Crusades began it was the German Emperor who led the Frankish hosts against
the Saracens. Charlemagne was a German Emperor, his capital was at Aachen within the present limits
of the German Empire and the language of his court was German. For several centuries after the
conquest of Gaul by the Franks their Teutonic tongue held its own against the Latin speech of the
Romanized Gauls.
The history of all Christian Europe is in some degree interwoven with this Holy Roman Empire.
Though the Empire was neither holy nor Roman but altogether secular and Teutonic, it was,
nevertheless, the heart of Europe for ages. Holland and Flanders, Lorraine and Alsace, Burgundy and
Luxemburg, Lombardy and the Veneto, Switzerland and Austria, Bohemia and Styria are states which
were originally component parts of the Empire although many of them have since been torn away by
rival nations or have become independent, while much of northern Italy remained under the sway of
Austria within the memory of living men.
The Empire wasted its strength in imperial ambitions and foreign conquests instead of
consolidating, organizing and unifying its own territories and the fact that the imperial crown was
elective for many generations before it became hereditary in the House of Hapsburg checked the
unification of Germany during the Middle Ages.
A strong hereditary monarchy, such as arose in England and in France, would have anticipated the
Germany of to-day by a thousand years and made it the predominant state in Christendom, but
disruptive elements in the persons of great territorial dukes were successful throughout its history in
preventing an effective concentration of power in the hands of the Emperor.
That the German Emperor was regarded, though vaguely, as the overlord of all Christian monarchs
was clearly indicated when Henry VIII of England and Francis I of France appeared as candidates for
the imperial crown against Charles of Spain, afterward the Emperor Charles V.
Europe was the Holy Roman Empire and the Holy Roman Empire was Europe predominantly until
the Thirty Years’ War. This war was perhaps the greatest catastrophe of all the ghastly crimes
committed in the name of religion. It destroyed an entire generation, taking each year for thirty years
the finest manhood of the nations.
Two-thirds of the population of Germany was destroyed, in some states such as Bohemia three-
fourths of the inhabitants were killed or exiled, while out of 500,000 inhabitants in Würtemberg there
were only 48,000 left at the end of the war. Terrible as this loss was, the destruction did not fall equally
on the various races and classes in the community. It bore, of course, most heavily upon the big blond
fighting man and at the end of the war the German states contained a greatly lessened proportion of
Nordic blood. In fact, from that time on the purely Teutonic race in Germany has been largely replaced
by the Alpine types in the south and by the Wendish and the Polish types in the east. This change of
race in Germany has gone so far that it has been computed that out of the 70,000,000 inhabitants of
the German Empire, only 9,000,000 are purely Teutonic in coloration, stature and skull characters.
The rarity of pure Teutonic and Nordic types among the German immigrants to America in contrast to
its almost universal prevalence among those from Scandinavia is traceable to the same cause.
In addition, the Thirty Years’ War virtually destroyed the land owning yeomanry and lesser gentry
formerly found in mediæval Germany as numerously as in France or in England. The religious wars of
France, while not as devasting to the nation as a whole as was the Thirty Years’ War in Germany,
nevertheless greatly weakened the French cavalier type, the “petite noblesse de province.” In Germany
this class had flourished and throughout the Middle Ages contributed great numbers of knights, poets,
thinkers, artists and artisans who gave charm and variety to the society of central Europe. But, as said,
this section of the population was practically exterminated in the Thirty Years’ War and this class of
gentlemen practically vanishes from German history from that time on.
When the Thirty Years’ War was over there remained in Germany nothing except the brutalized
peasantry, largely of Alpine derivation in the south and east, and the high nobility which turned from
the toils of endless warfare to mimic on a small scale the court of Versailles. After this long struggle the
boundaries in central Europe between the Protestant North and the Catholic South follow in a marked
degree the frontier between the northern plain inhabited chiefly by Nordics and the more mountainous
countries in the south populated almost entirely by Alpines.
It has taken Germany two centuries to recover her vigor, her wealth and her aspirations to a place in
the sun.
During these years Germany was a political nonentity, a mere congeries of petty states bickering and
fighting with each other, claiming and owning only the Empire of the Air as Napoleon happily phrased
it. Meantime France and England founded their colonial empires beyond the seas.
When in the last generation Germany became unified and organized, she found herself not only too
late to share in these colonial enterprises, but also lacking in much of the racial element and still more
lacking in the very classes which were her greatest strength and glory before the Thirty Years’ War. To-
day the ghastly rarity in the German armies of chivalry and generosity toward women and of knightly
protection and courtesy toward the prisoners or wounded can be largely attributed to this annihilation
of the gentle classes. The Germans of to-day, whether they live on the farms or in the cities, are for the
most part descendants of the peasants who survived, not of the brilliant knights and sturdy foot
soldiers who fell in that mighty conflict. Knowledge of this great past when Europe was Teutonic and
memories of the shadowy grandeur of the Hohenstaufen Emperors, who, generation after generation,
led Teutonic armies over the Alps to assert their title to Italian provinces, have played no small part in
modern German consciousness.
These traditions and the knowledge that their own religious dissensions swept them from the
leadership of the European world lie at the base of the German imperial ideal of to-day and it is for this
ideal that the German armies are dying, just as did their ancestors for a thousand years under their
Fredericks, Henrys, Conrads and Ottos.
But the Empire of Rome and the Empire of Charlemagne are no more and the Teutonic type is
divided almost equally between the contending forces in this world war. With the United States in the
field the balance of pure Nordic blood will be heavily against the Central Powers, which pride
themselves on being “the Teutonic powers.”
Germany is too late and is limited to a destiny fixed and ordained for her on the fatal day in 1618
when the Hapsburg Ferdinand forced the Protestants of Bohemia into revolt.
Although as a result of the Thirty Years’ War the German Empire is far less Nordic than in the
Middle Ages, the north and northwest of Germany are still Teutonic throughout and in the east and
south the Alpines have been thoroughly Germanized with an aristocracy and upper class very largely of
pure Teutonic blood.
VIII
THE EXPANSION OF THE NORDICS
The men of Nordic blood to-day form practically all the population of Scandinavian countries, as also
a majority of the population of the British Isles and are almost pure in type in Scotland and eastern and
northern England. The Nordic realm includes nearly all the northern third of France with extensions
into the fertile southwest; all the rich lowlands of Flanders; all Holland; the northern half of Germany
with extensions up the Rhine and down the Danube; and the north of Poland and of Russia. Recent
calculations indicate that there are about 90,000,000 of purely Nordic physical type in Europe out of a
total population of 420,000,000.
Throughout southern Europe a Nordic nobility of Teutonic type everywhere forms the old
aristocratic and military classes or what now remains of them. These aristocrats, by as much as their
blood is pure, are taller and blonder than the native populations, whether these be Alpine in central
Europe or Mediterranean in Spain or in the south of France and Italy.
The countries speaking Low German dialects are almost purely Nordic but the populations of High
German speech are very largely Teutonized Alpines and occupy lands once Celtic-speaking. The main
distinction between the two dialects is the presence of a large number of Celtic elements in High
German.
In northern Italy there is a large amount of Nordic blood. In Lombardy, Venice and elsewhere
throughout the country the aristocracy is blonder and taller than the peasantry, but the Nordic element
in Italy has declined noticeably since the Middle Ages. From Roman times onward for a thousand years
the Teutons swarmed into northern Italy, through the Alps and chiefly by way of the Brenner Pass.
With the stoppage of these Nordic reinforcements this strain seems to have grown less all through
Italy.[3]
3. Procopius tells a significant story which illustrates the contrast in racial character between the natives and the
barbarians. He relates that, at the surrender of Ravenna in 540 A. D. by the Goths to the army of the Byzantines, “when the
Gothic women saw how swarthy, small men of mean aspect had conquered their tall, robust, fair-skinned barbarians, they
were furious and spat in their husbands’ faces and cursed them for cowards.”
In the Balkan Peninsula there is little to show for the floods of Nordic blood that have poured in for
the last 3,500 years, beginning with the Achæans of Homer, who first appeared en masse about 1400 B.
C. and were followed successively by the Dorians, Cimmerians and Gauls, down to the Goths and the
Varangians of Byzantine times.
The tall stature of the population along the Illyrian Alps from the Tyrol to Albania on the south is
undoubtedly of Nordic origin and dates from some of these early invasions, but these Illyrians have been
so crossed with Slavs that all other blond elements have been lost and the existing population is
essentially of brachycephalic Alpine type. They are known as the Dinaric race. What few remnants of
blondness occur in this district, more particularly in Albania, as well as the so-called Frankish elements
in Bosnia, may probably be attributed to later infiltrations.
The Tyrolese seem to be largely Nordic except in respect to their round skull.
In Russia and in Poland the Nordic stature, blondness and long skull grow less and less pronounced as
one proceeds south and east from the Gulf of Finland.
It would appear that in all those parts of Europe outside of its natural habitat, the Nordic blood is on
the wane from England to Italy and that the ancient, acclimated and primitive populations of Alpine and
Mediterranean race are subtly reasserting their long lost political power through a high breeding rate
and democratic institutions.
In western Europe the first wave of the Nordic tribes appeared about three thousand years ago and
was followed by other invasions with the Nordic element becoming stronger until after the fall of Rome
whole tribes moved into its provinces, Teutonizing them more or less for varying lengths of time.
PROVISIONAL OUTLINE OF NORDIC INVASIONS AND METAL CULTURES
Russia, North
Great Germany France and M
B. C. Scandinavia Italy Greece, and Asia Minor Africa and
Britain and Austria Spain a
Balkans Egypt
Copper for
Co
Alpines ornaments,
(Hissarlik). 4000.
Neolithic. 3000 B. C. Founding of Copper
Rough Commencement Troy. systematically
Before Terramara
1. Neolithic pottery. Neolithic. Neolithic. of early Minoan Copper in mined, 3400.
3000 culture.
Domesticated in Crete. Cyprus. Pieces of iron
dog. Copper. Introduction from interior
of bronze of Great
from Egypt. Pyramid of
Gizeh, 3733.
Copper.
U
Copper. Great
Gizeh skulls;
Great expansion of
Alpine.
expansion of Alpines,
First
Alpines, introducing
3000– Bronze illustration of
2. introducing Copper. bronze into
2500 smelting. ship in Egypt,
bronze into north Italy.
2800.
Austria and Bronze
Pyramids,
later into introduced in
Memphis.
Germany. South from
Crete.
Great
expansion of
Eneolithic
Neolithic. Neolithic. Alpines,
culture.
introducing
bronze from
Su
Period of
Asia Minor. agricultural
Middle Minoan depression
in Crete, 2000– with
2500– Destruction of
3. Copper. 1800. invasions
1800 Hissarlik II.
Second city of from the
Hissarlik— desert.
2000. Feudal Age in
Egypt.
Transition from stone to

bronze.
Alpine
invasion
Alpine
Alpine invasion with bronze
invasion
with bronze culture in Early Nordic
with
culture France. invasions. Beginnings of Hyksos in K
bronze
4. 1800–1600 reaches Later, same Cnossos. Hittite Egypt, 1700.
culture.
Denmark and wave of Mycenæan Empire. First horses.
Round
southwest invasion culture.
Barrows.
Norway. enters
Megaliths.
Spain.
Megaliths.
K
1
Egyptian
First Aryan Empire at
Hallstatt iron
names of Thebes,
culture in
Late Minoan in deities— 1600–1150.
Austrian Fi
5. 1600–1400 Crete, 1600– Cappadocia. Egyptian
Tyrol has
1450. Hittite campaigns in
first
Empire with Asia.
beginning.
iron. Conquest of
Syria.
Full Bronze Last Minoan,
Age. 1450–1200.
Mycenæan
culture. Bronze.
Nordic Achæans
from south Hittites invade
Russia Syria.
Nordic Se
introduce Aryan Rameses II.
Villanova Phrygians.
6. 1400–1200 speech, 1400– 1230. Sea
culture. (Trojan
1300. Have iron peoples
leaders.)
swords. (Achæans)
1200. attack Egypt.
Transition from
bronze to iron
in Crete.
Hittites
Alpines
7. 1200–1000 Beginning of Hallstatt iron Cadiz founded c. 1100. Hallstatt iron. Armenians Phœnicia
cremation. culture in Spain, c. Umbrians and Trojan war, acquire supreme at
flourishes. 1100, by Oscans 1194–1184. Aryan sea.
Mixed Phœnicians. introduce first Nordic Hellenes tongue.
inhumation Aryan speech —Dorians—
and from enter Greece,
incineration. northeast. 1100.
Goidels Iron in Iron in full
occupy Etruria, 1100. development.
Germany.
1000.
Nordic
Nordic
Teutons cross
Goidels
from
cross Rhine
Scandinavia
and
to south
introduce
coasts of
Aryan
Baltic and to
speech
Denmark.
(Gaulish).
First invasion Zo
of Nordic
Teutons Hallstatt iron
from culture.
Scandinavia. Before 950
First First settlements Greek colonies
Other Celtic Phœnicians Iron common in Carthage
8. 1000–800 Nordics— on the site of in Asia
Nordics on masters of Greece. founded, 813.
Goidels. Rome. Minor.
Rhine and more than
Danube, half of
who Spain.
Celticized
the Alpines.
First iron
800 swords,
800.
The Goidels
are driven
In
south and
Expansion of
west by the
Mediterranean
Cymry. Iron Age in
Etruscans over
Expansion Russia.
Umbrians to
of the Megarian
Alps.
Cymry. colonization, Early Nordic
Legendary
First Aryan Pressure of Gauls in 700. raids.
9. 800–600 founding of
speech. Teutons in France. Greek colonies Cimmerians,
Rome, 753.
north. in Italy and 650.
First Greek
Last Goidels Sicily.
colonies in
expelled Appearance of
south Italy—
from Cimmerians.
Magna
Germany.
Græcia.
Iron swords
in Central
Europe.
La Tène iron
culture in
France.
Nordic
500. End of non-
Goidels
La Tène iron Aryan speech in
cross Persian N
culture. Crete.
First Pyrenees Nordic Gauls in conquest,
Cymric Invasion of Tyre under
Goidels in and valley of Po— 525.
10. 600–400 Belgæ Scythia by Babylonian
Ireland, introduce Cisalpine The last of
driven Darius, 512 B. yoke.
600. Aryan Gaul. the native
westward by C.
speech in Pharaohs.
Teutons. Persian wars,
Spain.
500–449.
First Gallic
money of
Marseilles,
silver.
La Tène
La Tène Iron.
iron.
La Tène iron
in Spain. Gauls under
Macedon
Cymric Brennus sack
conquers
Belgæ Rome, 382,
Greece, 338.
conquer and destroy Alexander
Celto-Scyths in Co
11. 400–300 northern Etruria. New conquers
Crimea, 4th
France. invasion of Egypt, 332.
century B. C.
Bronze Nordics into
Alexander the
money in Cisalpine
Great, 356–323.
western Gaul.
France.
Expansion
Great
of Teutons
expansion of
and
Nordic
expulsion of
Teutons out
Cymry as far
of
west as the
Scandinavia.
Weser.
12. 300–200 Cymric c. 250. First Gold coinage Expansion of Decline of Nordic
Belgæ— Teutons in in northeast Rome. Scythians in Galatians,
invasion, Austria. France. Russia, and 279.
c. 300. Gold, silver, Bronze appearance in
Known as and bronze coinage in Russia of Alpine
Brythons. money. the Sarmatians.
southwest. Nordic
Gaul fertile Galatians enter
and well Thrace and
cultivated. Greece—Delphi,
279; cross into
Asia Minor and
found Galatia.
Punic Wars,
264–146.
Teutons enter
Teutons drive
France.
Few Cymry Cymry out Slaves imported
Marius
or of Germany. in Rome to
13. 200–100 destroys
Brythons Teutons work the
Teutones
in Ireland. cross the latifundia.
and Cimbri,
Rhine.
100 B. C.
Augustus and
55. Julius
the
Cæsar. Cæsar
100 to organization
Copper conquers
14. Christian of the Roman
and iron Gaul, 59–
Era Empire.
money as 51.
Extinction of
currency.
old Romans.
Defeat of
Varus and Sarmatians
Roman appear in
15.
legions in Danube valley,
old Saxony, 50 A. D.
9 A. D.
These incoming Nordics intermarried with the native populations and were gradually bred out and the
resurgence of the old native stock, chiefly Alpine, has proceeded steadily since the Frankish
Charlemagne destroyed the Lombard kingdom and is proceeding with unabated vigor to-day. This
process was greatly accelerated in western Europe by the Crusades, which were extremely destructive to
the Nordic feudal lords, especially the Frankish and Norman nobility and was continued by the wars of
the Reformation and by those of the Revolution. The world war now in full swing with its toll of millions
will leave Europe much poorer in Nordic blood. One of its most certain results will be the partial
destruction of the aristocratic classes everywhere in northern Europe. In England the nobility has
already suffered in battle more than in any century since the Wars of the Roses. This will tend to realize
the standardization of type so dear to democratic ideals. If equality cannot be obtained by lengthening
and uplifting the stunted of body and of mind, it can be at least realized by the destruction of the exalted
of stature and of soul. The bed of Procrustes operates with the same fatal exactness when it shortens the
long as when it stretches the undersized.
The first Nordics in Spain were the Gauls who crossed the western Pyrenees about the end of the sixth
century before our era and introduced Aryan speech into the Iberian Peninsula. They quickly mixed with
Mediterranean natives and the composite Spaniards were called Celtiberians by the Romans.
In Portugal and Spain there are in the physical structure of the population few traces of these early
Celtic-speaking Nordic invaders but the Suevi, who a thousand years later occupied parts of Portugal,
and the Vandals and Visigoths, who conquered and held Spain for 300 years, have left some small
evidence of their blood. In the provinces of northern Spain a considerable percentage of light colored
eyes reveals these Nordic elements in the population.
Deep seated Castilian traditions associate aristocracy with blondness and the sangre azul, or blue
blood of Spain, probably refers to the blue eye of the Goth, whose traditional claim to lordship is also
shown in the Spanish name for gentleman, “hidalgo,” said to mean “the son of the Goth.” The fact that
the blood shows as “blue” through the fair Nordic skin is also to be taken into account.
As long as this Gothic nobility controlled the Spanish states during the endless crusades against the
Moors, Spain belonged to the Nordic kingdoms, but when their blood became impaired by losses in wars
waged outside of Spain and in the conquest of the Americas, the sceptre fell from this noble race into the
hands of the native Iberian, who had not the physical vigor or the intellectual strength to maintain the
world empire built up by the stronger race. For 200 years the Spanish infantry had no equal in Europe
but this distinction disappeared with the opening decades of the seventeenth century.
The splendid conquistadores of the New World were of Nordic type, but their pure stock did not long
survive their new surroundings and to-day they have vanished utterly, leaving behind them only their
language and their religion. After considering well these facts we shall not have to search further for the
causes of the collapse of Spain.
Gaul at the time of Cæsar’s conquest was under the rule of the Nordic race, which furnished the bulk
of the population of the north as well as the military classes elsewhere and, while the Romans killed off
an undue proportion of this fighting element, the power and vigor of the French nation have been based
on this blood and its later reinforcements. In fact, in the Europe of to-day the amount of Nordic blood in
each nation is a very fair measure of its strength in war and standing in civilization. The proportion of
men of pure type of each constituent race to the mixed type is also a powerful factor.
When, about 1000 B. C., the first Nordics crossed the lower Rhine they found the Mediterranean race
in France everywhere overwhelmed by an Alpine population except in the south. Long before the time of
Cæsar the Celtic language of these invaders had been imposed upon the entire population and the
country had been saturated with Nordic blood, except in Aquitaine which seems to have retained until at
least that date its Anaryan Iberian speech. These earliest Nordics in the west were known to the ancient
world as Gauls. These Gauls, or “Celts,” as they were called by Cæsar, occupied in his day the centre of
France. The actual racial complexion of this part of France was overwhelmingly Alpine then and is so
now, but this population had been Celticized thoroughly by the Gauls, just as it was Latinized as
completely at a later date by the Romans.
The northern third of France, that is above Paris, was inhabited in Cæsar’s time by the Belgæ, a Nordic
people of the Cymric division of Celtic speech. They were largely of Teutonic blood and in fact should be
regarded as the immediate forerunners of the Germans. They probably represent the early Teutons who
had crossed from Sweden and adopted the Celtic speech of their Nordic kindred whom they found on the
mainland. These Belgæ had followed the earlier Goidels across Germany into Britain and Gaul and were
rapidly displacing their Nordic predecessors, who by this time were much weakened by mixture with the
autochthones, when Rome appeared upon the scene and set a limit to their conquests by the Pax
Romana.
The Belgæ of the north of France and the Low Countries were the bravest of the peoples of Gaul,
according to Cæsar’s oft-quoted remark, but the claim of the modern Belgians to descent from this race
is without basis and rests solely on the fact that the present kingdom of Belgium, which only became
independent and assumed its proud name in 1831, occupies a small and relatively unimportant corner of
the land of the Belgæ. The Flemings of Belgium are Nordic Franks speaking a Low German tongue and
the Walloons are Alpines whose language is an archaic French.
The Belgæ and the Goidelic remnants of Nordic blood in the centre of Gaul taken together probably
constituted only a small minority in blood of the population, but were everywhere the military and ruling
classes. These Nordic elements were later reinforced by powerful Teutonic tribes, namely, Vandals,
Visigoths, Alans, Saxons, Burgundians and, most important of all, the Franks of the lower Rhine, who
founded modern France and made it for long centuries “la grande nation” of Christendom.
The Frankish dynasties long after Charlemagne were of purely Teutonic blood and the aristocratic
land owning and military classes down to the great Revolution were very largely of this type, which by
the time of the creation of the Frankish kingdom had incorporated all the other Nordic elements of old
Roman Gaul, both Gaulish and Belgic.
The last invasion of Teutonic-speaking barbarians was that of the Danish Northmen, who were, of
course, of unmixed Nordic blood and who conquered and settled Normandy in 911 A. D. No sooner had
the barbarian invasions ceased than the ancient aboriginal blood strains, Mediterranean, Alpine and
elements derived from Paleolithic times, began a slow and steady recovery. Step by step with the
reappearance of these primitive and deep rooted stocks the Nordic element in France declined and with
it the vigor of the nation. Even in Normandy the Alpines now tend to predominate and the French
blonds are becoming more and more limited to the northeastern and eastern provinces.
The chief historic events of the last thousand years have hastened this process and the fact that the
Nordic element everywhere forms the fighting section of the community caused the loss in war to fall
disproportionately as among the three races in France. The religious wars greatly weakened the Nordic
provincial nobility, which was before the Massacre of St. Bartholomew largely Protestant and the
extermination of the upper classes was hastened by the Revolutionary and Napoleonic wars. These last
wars are said to have shortened the stature of the French by four inches; in other words, the tall Nordic
strain was killed off in greater proportions than the little brunet.
When by universal suffrage the transfer of power was completed from a Nordic aristocracy to lower
classes predominantly of Alpine and Mediterranean extraction, the decline of France in international
power set in. In the country as a whole, the long skulled Mediterraneans are also yielding rapidly to the
round skulled Alpines and the average of the cephalic index in France has steadily risen since the Middle
Ages and is still rising.
The survivors of the aristocracy, being stripped of political power and to a large extent of wealth,
quickly lost their caste pride and committed class suicide by mixing their blood with inferior breeds. One
of the most conspicuous features of some of the French nobility of to-day is the strength of Oriental and
Mediterranean strains in them. Being for political reasons ardently clerical the nobility welcomes
recruits of any racial origin as long as they bring with them money and devotion to the Church.
The loss in war of the best stock through death, wounds or absence from home has been clearly shown
in France. The conscripts who were examined for military duty in 1890–2 were those descended in a
large measure from the military rejects and other stay-at-homes during the Franco-Prussian War. In
Dordogne this contingent showed seven per cent more deficient statures than the normal rate. In some
cantons this unfortunate generation was in height an inch below the recruits of preceding years and in it
the exemptions for defective physique rose from the normal six per cent to sixteen per cent.
When each generation is decimated or destroyed in turn a race can be injured beyond recovery but it
more frequently happens that the result is the annihilation of an entire class, as in the case of the
German gentry in the Thirty Years’ War. Desolation of wide districts often resulted from the plagues and
famines which followed the armies in old days but deaths from these causes fall most heavily on the
weaker part of the population. The loss of valuable breeding stock is far more serious when wars are
fought with volunteer armies of picked men than with conscript armies, because in the latter cases the
loss is more evenly spread over the whole nation. Before England resorted in the present war to
universal conscription the injury to her more desirable and patriotic classes was much more pronounced
than in Germany where all types and ranks were called to arms.
In the British Isles we find, before the appearance of the Nordic race, a Mediterranean population and
no important element of Alpine blood, so that at the present day we have to deal with only two of the
main races instead of all three as in France. In Britain there were, as elsewhere, representatives of earlier
races but the preponderant strain of blood was Mediterranean before the first arrival of the Aryan-
speaking Nordics.
Ireland was connected with Britain and Britain with the continent until times very recent in a
geological sense. The depression of the Channel coasts is progressing rapidly to-day and is known to
have been substantial during historic times. The close parallel in blood and culture between England and
the opposite coasts of France also indicates a very recent land connection, possibly in early Neolithic
times. Men either walked from the continent to England and from England to Ireland, or they paddled
across in primitive boats or coracles. The art of ship-building or even archaic navigation cannot go much
further back than late Neolithic times.
The Nordic tribes of Celtic speech came to the British Isles in two distinct waves. The earlier invasion
of the Goidels, who were still in the Bronze culture, arrived in England about 800 B. C. and in Ireland
two centuries later. It was part of the same movement which brought the Gauls into France. The later
conquest was by the Cymric-speaking Belgæ who were equipped with iron weapons. It began in the third
century B. C. and was still going on in Cæsar’s time. These Cymric Brythons found the early Goidels,
with the exception of the aristocracy, much weakened by intermixture with the Mediterranean natives
and would probably have destroyed all trace of Goidelic speech in Ireland and Scotland, as they actually
did in England, if the Romans had not intervened. The Brythons reached Ireland in small numbers only
in the second century B. C.
These Nordic elements in Britain, both Goidelic and Brythonic, were in a minority during Roman
times and the ethnic complexion of the island was not much affected by the Roman occupation, as the
legions stationed there represented the varied racial stocks of the Empire.
After the Romans abandoned Britain and about 400 A. D., floods of pure Nordics poured into the
islands for nearly six centuries, arriving in the north as the Norse pirates, who made Scotland
Scandinavian, and in the east as Saxons and Angles, who founded England.
The Angles came from somewhere in central Jutland and the Saxons came from coast lands
immediately at the base of the Danish Peninsula. All these districts were then and are now almost purely
Teutonic; in fact, this is part of old Saxony and is to-day the core of Teutonic Germany.
These Saxon districts sent out at that time swarms of invaders not only into England but into France
and over the Alps into Italy, just as at a much later period the same land sent swarming colonies into
Hungary and Russia.
The same Saxon invaders passed down the Channel coasts and traces of their settlement on the
mainland remain to this day in the Cotentin district around Cherbourg. Scandinavian sea peoples called
Danes or Northmen swarmed over as late as 900 A. D. and conquered all eastern England. This Danish
invasion of England was the same that brought the Northmen or Normans into France. In fact the
occupation of Normandy was probably by Danes and the conquest of England was largely the work of
Norsemen, as Norway at that time was under Danish kings.
Both of these invasions, especially the later, swept around the greater island and inundated Ireland,
driving both the Neolithic aborigines and their Celtic-speaking masters into the bogs and islands of the
west.
The blond Nordic element to-day is very marked in Ireland as in England. It is derived, to some
extent, from the early invaders of Celtic speech, but the Goidelic element has been very largely absorbed
in Ireland as in western England and in Scotland by the Iberian substratum of the population and is
found to-day rather in the form of Nordic characters in brunets than in the entirely blond individuals
who represent later and purer Nordic strains.
The figures for recruits taken some decades ago in the two countries would indicate that the Irish as a
whole are considerably lighter in eye and darker in hair color than are the English. The combination of
black Iberian hair with blue or gray Nordic eyes is frequently found in Ireland and also in Spain and in
both these countries is justly admired for its beauty, but it is by no means an exclusively Irish type.
The tall, blond Irishmen are to-day chiefly Danish with the addition of English, Norman and Scotch
elements, which have poured into the lesser island for a thousand years and have imposed the English
speech upon it. The more primitive and ancient elements in Ireland have always shown great ability to
absorb newcomers and during the Middle Ages it was notorious that the Norman and English colonists
quickly sank to the cultural level of the natives.
In spite of the fact that Paleoliths have not been found there some indications of Paleolithic man
appear in Ireland both as single characters and as individuals. Being, like Brittany, situated on the
extreme western outposts of Eurasia, it has more than its share of generalized and low types surviving in
the living populations and these types, the Firbolgs, have imparted a distinct and very undesirable aspect
to a large portion of the inhabitants of the west and south and have greatly lowered the intellectual
status of the population as a whole. The cross between these elements and the Nordics appears to be a
bad one and the mental and cultural traits of the aborigines have proved to be exceedingly persistent and
appear especially in the unstable temperament and the lack of coordinating and reasoning power, so
often found among the Irish. To the dominance of the Mediterraneans mixed with Pre-Neolithic
survivals in the south and west are to be attributed the aloofness of the island from the general trend of
European civilization and its long adherence to ancient forms of religion and even to Pre-Christian
superstitions.
In England, the same two ethnic elements are present, namely the Nordic and the Mediterranean.
There is, especially in Wales and in the west central counties of England, a large substratum of ancient
Mediterranean blood but the later Nordic elements are everywhere superimposed upon it.
Scotland is by race Anglian in the Lowlands and Norse in the Highlands with underlying Goidelic and
Brythonic elements, which are exceedingly hard to identify. The Mediterranean strain is marked in the
Highlands and is frequently associated with tall stature.
This brunetness in Scotland is, of course, derived from the same underlying Mediterranean stock
which we have found elsewhere in the British Islands.
The inhabitants of Scotland before the arrival of the Celtic-speaking Nordics seem to have been the
Picts, whose language was almost surely Non-Aryan. Judging from the remnants of Anaryan syntax in
the Goidelic and to a lesser degree in the Cymric languages, Pictish was related to the Anaryan Berber
tongues still spoken in North Africa. No trace of this Pre-Aryan syntax is found in English.
Where one race imposes a new language on another, the change is most marked in the vocabulary
while the ancient usage in syntax or the construction of sentences is the more apt to survive and these
ancient forms often give us a valuable clew to the aboriginal speech. This same Anaryan syntax is
particularly marked in the Irish language, a condition which fits in with the other Pre-Aryan usages and
types found there.
This divergence between the new vocabulary and the ancient habits of syntax is probably one of the
causes of the extreme splitting up of the various branches of the Aryan mother tongue.
Wales, like western Ireland, is a museum of racial antiquities and being an unattractive and poor
country has exported men rather than received immigration, while such invasions as did arrive came
with spent force.
The mass of the population of Wales especially in the upland or moorland districts is Mediterranean,
with a considerable addition of Paleolithic remnants. With changing social and industrial conditions
these Neolithic Mediterraneans are pushing into the valleys or towns with a resultant replacement of the
Nordic types.
Recent and intensive investigations reveal everywhere in Wales distinct physical types living side by
side or in adjoining villages unchanged and unchangeable throughout the centuries. Extensive blending
has not taken place though much crossing has occurred and the persistence of the skull shape has been
particularly marked. Such individuals as are of pure Nordic type are generally members of the old
county families and land owning class.
As to language in Wales, the Cymric is everywhere spoken in various dialects, but there are indications
of the ancient underlying Goidelic. In fact, Brythonic or Cymric may not have reached Wales much
before the Roman conquest of Britain. The earlier Goidelic survived in parts of Wales as late as the
seventh century but by the eleventh century all consciousness of race and linguistic distinctions had
disappeared in the common name of Cymry. This name should perhaps be limited to the Brythons of
England and not used for their kindred on the Continent.
In Cornwall and along the Welsh border racial types are often grouped in separate villages and the
intellectual and moral distinctions between them are well recognized.
The Nordic species of man in its various branches made Gaul the land of the Franks and made Britain
the land of the Angles and the Englishmen who built the British Empire and founded America were of
the Nordic and not of the Mediterranean type.
One of the most vigorous Nordic elements in France, England and America was contributed by the
Normans and their influence on the development of these countries cannot be ignored. The descendants
of the Danish and Norse Vikings who settled in Normandy as Teutonic-speaking heathen and who as
Normans crossed over to Saxon England and conquered it in 1066 are among the finest and noblest
examples of the Nordic race. Their only rivals in these characters were the early Goths.
This Norman strain, while purely Nordic, seems to have been radically different in its mental makeup,
and to some extent in its physical detail from the Saxons of England and also from their kindred in
Scandinavia.
The Normans appear to have been “fine race” to use a French idiom and their descendants are often
characterized by a tall, slender figure, much less bulky than the typical Teuton, of proud bearing and
with clearly marked features of classic Greek regularity. The type is seldom extremely blond and is often
dark. These Latinized Vikings were and are animated by a restless and nomadic energy and by a fierce
aggressiveness. They played a brilliant role during the twelfth and following centuries but later, on the
continent, this strain ran out, though leaving here and there traces of its former presence, notably in
Sicily where the grayish blue Sicilian eye called “the Norman eye” is still found among the old noble
families.
The Norman type is still very common among the English of good family and especially among
hunters, explorers, navigators, adventurers and officers in the British army. These latter-day Normans
are natural rulers and administrators and it is to this type that England largely owes her extraordinary
ability to govern justly and firmly the lower races. This Norman blood occurs often among the native
Americans but with the changing social conditions and the filling up of the waste places of the earth it is
doomed to a speedy extinction.
The Normans were Nordics with a dash of brunet blood and their conquest of England strengthened
the Nordic and not the Mediterranean elements in the British Isles, but the connection once established
with France especially with Aquitaine later introduced from southern France certain brunet elements of
Mediterranean affinities.
The upper class Normans on their arrival in England were probably purely Scandinavian, but in the
lower classes there were some dark strains. They brought with them large numbers of ecclesiastics who
were, for the most part drawn from the more ancient types throughout France. Careful investigation of
the graveyards and vaults in which these churchmen were buried revealed a large percentage of round
skulls among them.
In both Normandy and in the lowlands of Scotland there was much the same mixture of blood
between Scandinavian and Saxon but with a smaller amount of Saxon blood in France. The result in
both cases was the production of an extraordinarily forceful race.
The Nordics in England are in these days apparently receding before the Neolithic Mediterranean
type. The causes of this decline are the same as in France and the chief loss is through the wastage of
blood by war and through emigration.
The typical British soldier is blond or red bearded and the typical sailor is always a blond. The
migrating type from England is also chiefly Nordic. These facts would indicate that nomadism as well as
love of war and adventure are Nordic characteristics.
An extremely potent influence, however, is the transformation of the nation from an agricultural to a
manufacturing community. Heavy, healthful work in the fields of northern Europe enables the Nordic
type to thrive, but the cramped factory and crowded city quickly weed him out, while the little brunet
Mediterranean can work a spindle, set type, sell ribbons or push a clerk’s pen far better than the big,
clumsy and somewhat heavy Nordic blond, who needs exercise, meat and air and cannot live under
Ghetto conditions.
The increase of urban communities at the expense of the countryside is also an important element in
the fading of the Nordic type, because the energetic countryman of this blood is more apt to improve his
fortunes by moving to the city than the less ambitious Mediterranean.
The country villages and the farms are the nurseries of nations, while cities are consumers and seldom
producers of men. The effort now being made in America to settle undesirable immigrants on farms
may, from the viewpoint of race replacement, be more dangerous than allowing them to remain in
crowded Ghettos or tenements.
If England has deteriorated and there are those who think they see indications of such decline, it is
due to the lowering proportion of the Nordic blood and the transfer of political power from the vigorous
Nordic aristocracy and middle classes to the radical and labor elements, both largely recruited from the
Mediterranean type.
Only in Scandinavia and northwestern Germany does the Nordic race seem to maintain its full vigor in
spite of the enormous wastage of three thousand years of the swarming forth of its best fighting men.
Norway, however, after the Viking outburst has never exhibited military power and Sweden, in the
centuries between the Varangian period and the rise of Gustavus Adolphus, did not enjoy a reputation
for fighting efficiency. All the three Scandinavian countries after vigorously attacking Christendom a
thousand years ago disappear from history as a nursery for soldiers until the Reformation when Sweden
suddenly reappears just in time to save Protestantism on the Continent. To-day all three seem to be
intellectually anæmic.
Upper and Lower Austria, the Tyrol and Styria have a very considerable Nordic element which is in
political control but the Alpine races are slowly replacing the Nordics both there and in Hungary.
Holland and Flanders are purely Teutonic, the Flemings being the descendants of those Franks who
did not adopt Latin speech as did their Teutonic kin across the border in Artois and Picardy; and
Holland is the ancient Batavia with the Frisian coast lands eastward to old Saxony.
Denmark, Norway and Sweden are purely Nordic and yearly contribute swarms of a splendid type of
immigrants to America and are now, as they have been for thousands of years, the chief nursery and
broodland of the master race.
In southwestern Norway and in Denmark, there is a substantial number of short, dark round heads of
Alpine affinities. These dark Norwegians are regarded as somewhat inferior socially by their Nordic
countrymen. Perhaps as a result of this disability, a disproportionately large number of Norwegian
immigrants to America are of this type. Apparently America is doomed to receive in these later days the
least desirable classes and types from each European nation now exporting men.
In mediæval times the Norse and Danish Vikings sailed not only the waters of the known Atlantic, but
ventured westward through the fogs and frozen seas to Iceland, Greenland and America.
Sweden, after sending forth her Goths and other early Teutonic tribes, turned her attention to the
shores of the eastern Baltic, colonized the coast of Finland and the Baltic provinces and supplied also a
strong Scandinavian element to the aristocracy of Russia.
The coast of Finland is as a result Swedish and the natives of the interior have distinctly Nordic
characters with the exception of the skull, which in its roundness shows an Alpine cross.
The population of the so-called Baltic provinces of Russia is everywhere Nordic and their affinities are
with Scandinavia and Germany rather than with Slavic Moscovy. The most primitive Aryan languages,
namely, Lettish, Lithuanian and the recently extinct Old Prussian, are found in this neighborhood and
here we are not far from the original Nordic homeland.

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Electrochemical Methods:

Fundamentals and Applications, 2nd

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Ещ equilibrium potential of an electrode V 1.3.2,3.4.1

AG° standard Gibbs free energy change in a kJ, kJ/mol 2.1.2,2.1.3

Ч limiting current A 1.4.2

L length of a porous electrode 11.6.2

(b) resistance ft 10.1.2

(a) transfer coefficient none 3.3

(b) transmission coefficient of a reaction none 3.1.3

outer component of the reorganization eV 3.6.2

ADC analog-to-digital converter 15.8

betters may be subscripted i, q, or r to indicate irreversible, quasi-reversible, or reversible reactions.

EC heterogeneous electron transfer followed by homogeneous 12.1.1

1.1.1 Electrochemical Cells and Reactions

Zn/Zn 2 + , СГ/AgCl/Ag (l.l.l)

Pt/H2/H+, СГ/AgCl/Ag (1.1.2)

Electrode Solution Electrode Solution

Electrode Solution Electrode Solution

Consider a typical electrochemical experiment where a working electrode and a ref-

Pt/H+, ВГ(1 M)/AgBr/Ag Cathodic

Cell Potential Anodic

Hg/I-Г, ВГ(1 M)/AgBr/Ag

0.5 -0.5 -1.5

Potential (V vs. NHE)

Hg/I-Г, ВГ(1 М), Cd2+(1mM)/AgBr/Ag

1.1.2 Faradaic and Nonfaradaic Processes

1.2 NONFARADAIC PROCESSES AND THE NATURE OF THE

Hg + С Г -> |Hg 2 Cl 2 + e (at ~ +0.25 V vs. NHE) (1.2.1)

1.2.2 Capacitance and Charge of an Electrode

Metal Solution Metal Solution

Figure 1.2.2 The metal-solution

1.2.3 Brief Description of the Electrical Double Layer

Specifically adsorbed anion

- Metal — > Ц Solution >-

1.2.4 Double-Layer Capacitance and Charging

Cd is generally a function of potential, the proposed model in terms of circuit elements is

(a) Voltage (or Potential) Step

Noting that / = dq/dt and rearranging yields

Figure 1.2.6 Potential step experiment for an RC

Figure 1.2.7 Current

(b) Current Step

E = iRK + 4r\ dt (1.2.11)

(c) Voltage Ramp (or Potential Sweep)

Figure 1.2.8 Current step experiment for an RC

_ Figure 1.2.9 E-t behavior resulting

Figure 1.2.10 Current-time

No proper understanding is possible of the meaning of the history of Christendom or full

Transition from stone to

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