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Chapter!1!
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!Introduction!to!Electrochemistry!and!
Electrochemical!Products!
!
# Modern# life# relies# on# batteries# to# power# laptop# computers,# and# sub;100;nm#
thick# copper# interconnects# that# join# transistors# on# the# logic# chips# are# at# the# heart# of#
these#computers.##Furthermore,#health#care#increasingly#relies#on#biosensors#for#patient#
monitoring# and# for# diagnostics.# # For# example,# glucose# sensors# have# dramatically#
improved# the# life# of# diabetics.# # And# because# of# environmental# concerns,# many# have#
great#hopes#for#fuel#cells#and#for#novel#batteries#
that# will# make# wind# and# solar# energy# more# Main!Point!
feasible#when#scaled#to#a#significant#fraction#of# #
the# global# supply.# # Batteries,# fuel# cells,# some# Electrochemical# technologies# are#
biosensors,# and# some# of# the# key# a# vital# part# of# modern# life.##
microfabrication# processes# used# for# advanced# Advances# require# talented#
computer# chips# are# electrochemical# scientists#and#engineers.#
technologies,#the#subject#of#this#text.#
Electrochemistry# is# the# branch# of# science# that# focuses# on# charge;transfer#
reactions# that# occur# at# the# interface# between# an# ionically# conducting# phase# and# an#
electronically# conducting# phase.# # Electrochemists# and# electrochemical# engineers# may#
also# study# the# consequence# of# these# reactions# and# may# consider# how# different#
materials#and#conditions#can#affect#reaction#rates.###Figure#1.1#shows#a#representation#of#
an#interface.##The#overall#rate#depends#not#only#on#the#charge;transfer#kinetics,#but#also#

Electrochemistry-and-Electrochemical-Engineering.-An-Introduction-by#Alan#C.#West# 1#
Chapter#1.##Introduction#to#Electrochemistry#and#Electrochemical#Products#

transport# processes# through# the# electrolyte,# with# possible# added# resistances# due# to# a#
gas# phase# reactant# or# product# and# from# solid# films# that# may# form# on# the# electrode#
surface.#

Figure! 1.1.# # Schematic# diagram# of# an# electrode# process,# where# electrons# are#
delivered#through#the#electron;conducting#phase.#The#electrolyte#is#ion#conducting,#
and# reactants# are# transported# to# the# interface,# where# charge# transfer# occurs.# # In#
this# case,# the# reduction# of# ferric# ions# to# ferrous# ions# is# depicted.# # Charge# transfer#
occurs# over# very# small# distances.# # For# a# common# system# used# in# electrochemical#
studies,# the# layer# over#which# significant# concentration# variations# arise# may# be# on#
the#order#of#10;20#microns#for#moderate#flows.#

# Alessandro#Volta,#who#is#credited#with#inventing#the#first#battery#in#the#1790s,#
is# often# considered# a# founder# of# the# field.# # # Over# the# next# century,# rapid# progress# was#
made,#and#the#Electrochemical#Society,#an#organization#of#scientists#and#engineers#with#
a# mission# that# includes# the# advancement# of# theory# and# practice# at# the# forefront# of#
electrochemistry,#has#been#in#existence#since#1902.1#The#very#early#establishment#and#
success#of#the#society#was#in#part#because#of#the#industrial#importance#of#electrolysis.##
Electrochemical#processes#remain#the#primary#mode#of#producing#commodities#such#as#
chlorine,# sodium# hydroxide,# and# aluminum.# # # # The# key# overall# reaction# of# the# chlor;
alkali# industry# is# conversion# of# aqueous# NaCl# to# Cl2# gas# and# concentrated# aqueous#
NaOH:#

2#NaCl#(aq)#+#2#H2O##Cl2(g)#+#2NaOH(aq)#+#H2(g)# (1)#

This# is# achieved# most# economically# via# an# electrochemical# process# depicted# in# figure#
1.2,# in# which# chloride# anions# are# oxidized# at# the# anode,# and# water# is# reduced# at# the#
cathode.:# #

2Cl;#(aq)###Cl2#(g)#+##2e;# (2)#

# #

2#
 2H2O#+#2e;###2OH;#(aq)#+##H2(g)# # (3)#

The#concentrated#aqueous#NaOH#solution#is#processed#further#to#evaporate#a#fraction#of#
the# water.# # As# commodity# chemicals,# process# design# would# focus# on# minimizing#
operating#costs#and#controlling#the#purity#of#chemicals.####

Note:! ! Electrochemical# reactions,# as# depicted# in# equations# 1;3# are# sometimes#
written#in#a#short;hand#notation#as#:#
#
# # Pt(s)|Cl2(g)|NaCl(aq)||NaOH(aq)|H2(g)|#Pt(s)#
#
where# Pt# is# taken# to# be# used# for# the# electrode,# even# though# another# metal# is#
probably#used#in#practice.# #The# double#vertical# lines# are#meant#to# convey#a#region#
where#a#transition#from#one#electrolyte#composition#to#another#takes#place.##This#is#
a#non;equilibrium#situation,#leading#to#transport#properties#sometimes#influencing#
experiments# intended# to# measure# thermodynamic# properties.# # This# potential,#
sometimes#called#a#liquid;junction#potential,#can#be#designed#to#be#a#reproducible,#
small# correction,# which# can# be# understood# from# basic# transport# analysis# of# ionic#
diffusion#and#migration.#This#notation#is#convenient#for#an#experienced#person,#but#
can#be#initially#confusing.##Problem#1.8#provides#some#examples,#and#the#notation#is#
used#more#in#chapter#4.#
#
Despite# its# early# prominence# in# the# chemical# industry,# electrochemical#
technologies#are#not#discussed#as#part#of#the#standard#chemical#engineering#curriculum,#
at# least# in# the# United# States.# # # # As# early# as# 1991,# it# was# pointed# out# that# discussion# of#
electrochemistry#within#standard#physical#chemistry#courses#is#also#very#limited.2##Yet#
electrochemical#products#continue#to#be#used#to#satisfy#diverse#societal#needs,#such#as#
energy#storage#and#conversion,#biosensors,#and#advanced#manufacturing.###
We#call#the#reactions#2#and#3#“electrochemical#reactions”#because#electrons#are#
reactants#at#the#cathode#and#products#at#the#anode.##So#what’s#the#big#deal?##Is#this#not#
just#an#example#of#a#chemical#reactor#in#which#two#heterogeneous#reactions#proceed?##
Is# there# nothing# more# to# achieving# a# successful# design# than# optimization# of# two# solid#
substrates#where#the#interfacial#reactions#proceed?#
# ##Well,# yes# and# no.# # For# example,# rates# of# heat# and# mass# transfer,# which# are#
strongly# influenced# by# mixing,# must# be# considered# for# both# chemical# and#
electrochemical#reactors.##However,#in#the#electrochemical#reactor,#electrolytic#current#
results#from#carrying#out#the#reduction#and#oxidation#reactions#on#spatially#separated#
surfaces.##This#leads#to#several#possible#electrical;field#effects#that#may#require#careful#
attention.#Design#principles#based#on#the#fundamentals#of#chemical;reactor#engineering#
and# transport# phenomena# remain# relevant.# # But# a# background# in# electrochemistry#
allows#for#a#more#comprehensive#analysis,#including#the#treatment#of#phenomena#that#
may# be# unique# to# electrochemical# systems.# # Let# us# illustrate# with# an# example# that#
demonstrates# that# sometimes# we# need# to# consider! both! the! chemical! and! electrical!
nature!of!an!electrochemical!system.#

3#
Chapter#1.##Introduction#to#Electrochemistry#and#Electrochemical#Products#

Figure!1.2.##Schematic#of#an#electrolytic#cell,#where#chlorine#gas#is#produced#at#the#
anode# and# hydrogen# gas# at# the# cathode.# # The# evolution# of# hydrogen# makes# the#
catholyte#more#alkaline#by#producing#hydroxyl#ions.##
#
#
!
1.1.!!Example:!Electrodeposition!on!a!Silicon!Wafer!
As#part#of#a#multi;step#manufacturing#line,#a#process#is#required#to#electroplate#
a#one;micron;thick#film#of#copper#on#the#surface#of#a#300;mm#silicon#wafer,#upon#which#
a# perfectly# conductive†# layer# has# been# pre;deposited# by# a# chemical# process# known# as#
electroless#deposition.##The#electrodeposition#is#achieved#via#the#reduction#reaction#

!
( )
Cu2+ aq !+!2!e) → Cuo # (4)#

In#addition#to#the#cathodic#reaction#4,#there#must#also#be#an#anodic#reaction#to#complete#
the#electrochemical#cell.##This#reaction#may#be#the#reverse#of#reaction#4#if#a#copper#or#
copper;alloy# anode# is# used# or# could# be,# for# example,# O2# evolution,# if# a# Pt# anode# were#
employed:#
(5)#
!
1
() ( )
H2O! → O2 g !+!2H+ aq !+!2e+ #
2
The#choice#of#anode#material#may#be#influenced#by#multiple#factors,#but#for#the#present#
illustration#we#focus#on#the#cathode.#

########################################################
†
For#wafers#with#very#thin#seed#layers,#it#may#not#be#a#good#assumption#that#the#wafer#is#a#perfect#
conductor.##An#example,#where#the#substrate#is#not#a#perfect#conductor,#is#discussed#in#chapter#6.#

4#
 We#assume#that#an#important#constraint#is#that#the#minimum#Cu;film#thickness#
at#any#point#on#the#wafer#must#be#greater#than#0.9#microns,#and#the#maximum#thickness#
must# be# less# than# 1.1# microns.# # First,# one# can# ask# why# would# there# exist# spatial#
variations# in# thickness?# # The# thickness# is# related# to# the# local# current# density# [A# cm;2]#
and#the#total#deposition#time#via#a#conversion#between#moles#and#the#coulombic#charge#
of#a#mole#of#electrons.##This#relationship#is#known#as#Faraday’s#law#and#is#discussed#in#
chapter#2.##Design#to#achieve#thickness#uniformity#is#therefore#the#same#as#designing#to#
achieve# spatial# uniformity# of# a# reaction# rate,# a# task# that# a# chemical# engineer# may#
encounter#in#a#variety#of#applications.#
#

Note:! # Faraday’s# law# is# exact# as# long# as# the# current# efficiency# is# 100%,# where# the#
current#efficiency#is#a#measure#of#the#fraction#of#current#that#goes#into#the#desired#
reaction.# # For# Cu# electrodeposition,# it# is# not# uncommon# to# achieve# current#
efficiencies# greater# than,# for# example,# 98%.# # For# the# electrodeposition# of# a# metal#
such#as#gold,#it#is#not#unusual#to#plate#at#a#current#efficiency#of#50%,#with#much#of#
the#remaining#current#resulting#in#the#reduction#of#water#to#hydrogen#gas.#

#
Carrying#out#reaction#4#in#an#electrolyte#containing#CuSO4#and#H2SO4# may#yield#
films# with# excellent# material# properties# if- the# operating# conditions# are# properly#
controlled.# # The# CuSO4# is# present# as# a# source# of# cupric# ions,# and# the# sulfuric# acid# is#
known# sometimes# as# the# “supporting# electrolyte;”# the# supporting# electrolyte# is#
important,# even# though# it# is# not# directly# involved# in# reaction# 4.# # Often# the# role# of#
supporting# electrolyte# is# clearly# understood# from# first# principles,# but# sometimes# the#
precise# reason# for# selecting# one# supporting# electrolyte# is# simply# known# by# empirical#
observations#such#as#the#superior#material#properties#of#the#Cu#film#obtained#by#plating#
in#an#acid;copper#bath.##As#in#any#discipline,#experience#can#help!#
To# proceed# with# the# development# of# a# process# for# plating# on# the# 300;mm#
wafer,#the#best#operating#conditions#were#identified#through#beaker;scale#experiments.##
A#rotating#disk#electrode#(RDE),#shown#in#figure#1.3,#was#used#because#it#is#particularly#
convenient,#as#discussed#in#more#detail#in#chapter#7.##A#key#advantage#of#the#RDE#is#that#
the#rotation#of#the#electrode#creates#a#well;understood#and#easily#controlled#fluid#flow#
that#results#in#a#uniform#mass#transfer#rate.##

Note:!!#The#limiting#current#density#is#the#maximum#rate#at#which#an#electrochemical#
reaction#can#proceed#due#to#mass;transfer#limitations.##Typically,#the#limiting#current#
arises# because# the# reactant# concentration# drops# to# zero# at# the# interface.# # Further#
increases#in#applied#potential#do#not#result#in#an#increase#in#the#reaction#rate,#at#least#
until#a#potential#is#reached#at#which#another#electrochemical#reaction#can#proceed.#
#

Using#an#RDE#with#disk#radius#ro#=#1.5#mm,#the#engineer#discovered#conditions#
that#yielded#a#film#with#desirable#material#properties.##The#film#thickness#was#found#to#
be#uniform#to#within#one#percent,#well#within#the#design#constraint.##Furthermore#the#
ratio# of# the# average# interfacial# reaction# rate# to# the# “limiting# current# density”# ilim# was#
found#to#be# iavg / ilim ≈ 0.1 .##This#limiting#current#density#is#a#measure#of#when#the#rate#of#
!
reaction# 4# is# limited# by# mass# transfer# of# cupric# ions# to# the# electrode# surface.# # When#
working#at#such#a#small#fraction#of#the#limiting#current#density,#mass;transfer#processes#
do#not#significantly#impact#the#rate#of#the#interfacial#reaction.##

5#
Chapter#1.##Introduction#to#Electrochemistry#and#Electrochemical#Products#

Figure! 1.3.# # Side# and# top# views# of# a# rotating# disk# electrode.# # The# electrode# is#
constructed#in#the#center#of#an#insulating#material,#and#the#entire#assembly#can#be#
rotated.##The#rotational#motion#induces#a#well;controlled,#easily#reproducible#fluid#
flow#that#brings#reactant#uniformly#through#the#electrolyte#to#the#electrode#surface.##
The#electrons#are#typically#transported#through#a#(rotating)#shaft.#
#
# #
Based# on# experience# with# the# electroless;deposition# process,# the# engineer#
thought#that#the#scale;up#should#be#straightforward,#at#least#in#terms#of#understanding#
the# mass# transfer# of# reactant# in# the# larger# system.# However,# when# the# scale# up# was#
attempted,#the#film#thickness#was#found#to#be#very#non;uniform#as#seen#in#figure#1.4.##If#
indeed#the#reaction#4#were#identical#in#behavior#to#a#heterogeneous#chemical#reaction,#
this#is#a#surprising#result.###
However,# if# one# considers# the# electrochemical# process# from# the# viewpoint# of#
applying# an# electrical# current,# one# may# expect# a# significant# “edge# effect”# for# flow# of#
current#through#a#resistive#medium#to#a#perfectly#conducting#disk.3##In#such#a#case,#the#
non;uniform# curve# in# figure# 1.4# may# be# anticipated,# and# the# uniform# thickness# result#
obtained#on#the#smaller#electrode#may#instead#be#surprising.###In#fact,#multiple#factors#
influence# scaling# of# a# process.# These# complex# situations# can# be# readily# understood#
through#application#of#electrochemical#fundamentals#as#discussed#throughout#the#text.#

6#
 2

1.8

1.6
film%thickness,%µm

1.4

1.2
r %=%1.5%mm
o
1

0.8
ro%=%150%mm
0.6

0.4
0 0.2 0.4 0.6 0.8 1

r/ro
#

Figure!1.4.##Film#thickness#of#electrodeposited#copper#as#a#function#of#dimensionless#
distance#on#a#disk#electrode#or#wafer.###When#deposited#on#the#electrode#with#a#small#
radius,#thickness#is#very#uniform.##On#the#larger#electrode,#the#thickness#at#the#center#
of#the#wafer#is#only#one#half#the#anticipated#the#value.##Clearly,#the#design#constraints#
are#not#satisfied#in#this#case,#and#the# electrolyte,#the#reactor,# or#both# need#to# be#re;
designed.#
#

Note:!As#the#characteristic#length#scale#increases,#the#spatial#variation#in#reaction#rate#
tends#to#increase.##The#degree#of#increase#depends#on#the#ratio#of#resistances.##Problem#
2.14#provides#an#example#calculation#showing#how#reaction#rate#may#vary#in#a#single#
cylindrical#pore.##In#electrochemical#design#and#analysis,#we#consider:#
#
• the#ratio#of#a#charge;transfer#resistance#to#mass;transfer#resistance#
• the#ratio#of#a#charge;transfer#resistance#to#ohmic#resistance#
#
# # Regardless# of# which# ratio# is# dominating# the# scaling,# the# current# distribution#
tends# to# become# more# nonuniform# with# size.# # For# many# engineers,# the# increase# in#
nonuniformity#with#size#is#intuitive,#but#the#details,#discussed#throughout#subsequent#
chapters,#may#not#be.#
#
!
1.2.!!Concepts!
Engineers# and# scientists# from# multiple# disciplines# design,# develop,# and#
characterize#electrochemical#systems.##The#focus#is#often#understanding#and#designing#

7#
Chapter#1.##Introduction#to#Electrochemistry#and#Electrochemical#Products#

systems# that# allow# interfacial# processes# to# occur# efficiently# at# high# rates.# # Sometimes,#
we# want# to# minimize# rates.# # For# example,# we# want# to# minimize# corrosion# rates# or#
electrolyte;degradation#rates.##Nevertheless,#the#focus#is#on#rate,#and#this#focus#on#rate#
phenomena# is# also# an# attribute# of# chemical# engineering,4# the# author’s# discipline.# A#
traditional# chemical# engineering# framework# therefore# influences# the# text,# where#
conceptual# foundations# are# organized# into# reaction# kinetics# and# reactor# design,#
transport#phenomena,#and#thermodynamics.#
Understanding#how#to#control#and#predict#chemical;reaction#rates#and#how#to#
design#reactors#that#allow#for#safe#and#economic#production#of#chemicals#and#materials#
is# important.# A# wide# swath# of# engineers# and# scientists# are# thus# familiar# with# the#
principles# of# chemical# kinetics# and# reactor# design# for# purposes# of# “scaling# up”# a#
process.###

Note:!!#When#we#talk#about#scale;up,#we#include#“scale;down,”#where#one#focuses#
on#making#the#system#smaller.##Engineers#may#be#just#as#often#tasked#with#making#a#
product#or#process#smaller#for#applications#such#as#advanced#sensors,#miniaturized#
power#systems,#and#microfabrication.##
#
#Even# within# the# context# of# a# scientific# research# laboratory,# scale# up# or#
scale# down# of#a#process#is#important#because#it#may# allow# for# novel#experiments.##
The# use# of# microfluidic# designs# or# microelectrodes,# for# example,# may# allow# for#
measurements#of#reaction#rates#at#short#time#scales,#possibly#without#interference#
from#transport#limitations.#
# #
Fundamentally,# the# scale# up# of# an# electrochemical# reactor# requires# a#
consideration#of#reaction#kinetics.##A#reaction#often#proceeds#along#a#path#in#which#an#
intermediate# configuration# in# a# chemical# transformation# is# in# an# energetically#
unfavored# state.# # This# leads# to# the# concept# of# an# energy# of# activation# or# a# transition#
state,# and# an# Arrhenius# or# Arrhenius;like# equation# can# be# introduced.# In#
electrochemistry,# we# can# modify# the# Arrhenius# equation# by# assuming# that# activation#
energy#is#a#function#of#an#electrical#potential.##This#leads#to#a#Butler;Volmer#equation,#
which#is#probably#the#most#important#new#idea#introduced#in#chapter#3.###

As# with# reacting# chemical# systems,# electrochemical# rate# laws# (for# example,#
dependence#of#rate#on#reactant#concentration#to#the#first#power)#can#also#be#connected#
with# reaction# mechanisms.# # This# can# lead# to# modifications# to# the# Butler;Volmer#
equation# and# allows# for# the# construction# of# models# connecting# interfacial# kinetics# to#
transport#phenomena#and#thermodynamics.#

Note:! ! # Interestingly,# in# electrochemical# kinetic# studies,# the# rate# of# reaction# is#
measured#directly# by#using# an#ammeter#to# quantify# the# flow# rate#of#electrons# (the#
current)# through# the# electrical# leads# to# the# electrodes.# # Devices# are# available# for#
measurement# of# very# small# currents# with# great# accuracy.# In# more# conventional#
chemical# reactions,# rates# are# inferred# by,# for# example,# measuring# variations# of#
concentration#of#reactant#or#product#with#time.#The#ease#in#measuring#reaction#rate#
makes#electrochemistry#attractive#for#chemical#and#biochemical#sensors.###

8#
# Thermodynamic# analysis# is# powerful# for# exploring# new# ideas,# understanding#
observations,#and#organizing#data.##As#for#chemical#kinetics#and#transport#phenomena,#
thermodynamics#is#studied#by#a#very#large#number#of#engineers#and#scientists.##And#as#
for# these# other# subjects,# additional# ideas,# which# only# a# much# smaller# set# of# scientists#
considers#in#detail,#are#required#for#rigorous#treatment#of#electrochemical#phenomena.###
Some# of# the# concepts# that# emerge# are# subtle,# but# rapid# progress# with# the# most# basic#
ideas#is#achievable.#
Once# thermodynamics# is# introduced,# the# question# concerning# whether#
electrochemical#systems#are#really#unique#can#be#revisited#from#a#different#perspective.##
If# we# describe# the# propensity# for# a# reaction# to# proceed# in# terms# of# chemical# (or#
electrochemical)# potentials,# then# electrons# can# be# treated# like# any# other# reactant# or#
product,# realizing# that,# since# they# are# charged,# they# respond# to# an# electrical# state.##
However,#from#a#practical#perspective#it#may#be#convenient#to#split#this#electrochemical#
potential# into# a# chemical# potential# and# an# electrical# potential,# where# the# “electrical#
state”# is# represented# by# an# electrical# potential# that# is# similar# to# the# electrostatic#
potential# introduced# in# basic# physics.# # Once# this# viewpoint# is# taken,# electrochemical#
systems#do#indeed#appear#to#be#different#from#chemical#systems.###
Electrochemical# reactions# occur# at# interfaces# between# electronically# and#
ionically# conducting# phases.# # Reactants# and# or# products# must# be# transported# through#
the#electrolyte#(and#sometimes#also#a#gas#phase).##The#rate#of#mass#transfer#is#a#strong#
function# of# convection# and# diffusion,# as# is# also# the# case# for# non;charged# species.# # An#
electrical# field# also# influences# the# motion# of# ionic# species# through# # “electrical#
migration.”# This# additional# contribution# is# sometimes# difficult# to# treat# because# the#
electrical# field# is# not# a- priori# known# but# instead# also# depends# on# the# concentration#
fields.# # This# leads# to# nonlinear# governing# equations# that# must# be# solved# in# a# coupled#
manner.##These#considerations#are#discussed#in#chapter#5#and#further#in#chapter#6.#
In# chapter# 7,# concepts# within# the# context# of# the# rotating# disk# electrode# are#
demonstrated.##The#rotating#disk#electrode#is#very#simple#and#is#often#a#workhouse#in#
research#laboratories#because#the#mass#transfer#rates#resulting#from#the#rotation#can#be#
reproducibly#controlled#over#a#very#large#range.##Perhaps#as#importantly,#it#is#very#easy#
to#use#when#compared#to#alternative#means#of#creating#flow.#
#Chapter# 8# also# reinforces# these# ideas# through# an# introduction# to#
electroanalytical# methods.# # There# exists# a# large# number# of# methods# that# have# been#
developed# and# used,5# and# a# detailed# inventory# of# different# approaches# is# beyond# the#
scope# of# the# present# text.# Even# for# a# design# engineer,# who# will# never# work# in# an#
electrochemistry# laboratory,# an# introduction# to# electroanalytical# methods# may# be#
valuable# because# they# are# utilized# to# obtain# kinetic,# transport,# and# thermodynamic#
properties# of# electrochemical# systems.# # Furthermore,# electrochemical# methods# are#
sometimes#the#superior#approach#to#obtain#thermodynamic#and#transport#parameters#
even#when#the#substance#is#not#utilized#within#an#electrochemical#process.#
# We# also# demonstrate# concepts# within# the# context# of# the# design# of#
electrochemical# reactors# (chapter# 6)# and# porous# electrodes# (chapter# 9).# # # Building# on#
fundamentals,# modeling# approaches# and# dimensionless# groups# are# discussed.# # While#
chapters# 6# and# 9# deal# with# scale# up,# chapter# 10# provides# some# considerations# of# the#
choice# of# electrode# material# or# electrolyte# composition,# as# driven# by# product#
requirements.##Instead#of#attempting#to#provide#a#general#approach,#we#write#chapter#
10#from#a#case;study#perspective.#
Finally,# in# part# because# electrochemical# biosensors# represent# an# important#
class# of# electrochemical# products,# chapter# 11# provides# a# brief# introduction# through#

9#
Chapter#1.##Introduction#to#Electrochemistry#and#Electrochemical#Products#

design#examples,#of#work#at#the#interface#between#electrochemistry#and#biology.##It#is#
hard#to#work#in#a#scientific#discipline#or#an#industry#that#is#not#touched#by#an#infusion#
of#biological#applications.##The#electrochemical#sciences#are#no#different,#and#there#have#
been#emerging#uses#beyond#biosensors.###
Throughout# the# text,# we# provide# examples# where# our# students# have# found#
employment# and# our# academic# colleagues# have# concentrated# research# efforts.# # # We#
therefore# focus# on# electrochemical# products.# # # This# does# not# mean,# for# example,# that#
aluminum#refining#or#lead;acid#starter#batteries#are#not#economically#important.##They#
do# remain# relevant,# and# a# fundamental# knowledge# of# electrochemistry# and#
electrochemical#engineering#will#allow#contributions#to#these#mature#industries.###
-
Note:! ! # Corrosion# is# also# commercially# of# great# importance,# with# a# small# but#
significant# fraction# of# a# country’s# resources# required# to# prevent# it# and# to# replace#
materials#that#deteriorate#due#to#it.##Concepts#from#electrochemistry#play#a#key#role#
in#studying#corrosion#processes#and#products,#such#as#new#materials#and#coatings#
designed#to#slow#the#rate#of#corrosion.###
#
Electroless# deposition# is# analogous# to# corrosion# in# the# sense# that# a#
reduction#and#oxidation#reaction#occurs#on#the#same#surface.##In#this#case,#a#metallic#
ion# that# is# reduced# (deposited)# is# in# the# same# electrolyte# as# a# reducing# agent.##
Substantial#electrolyte#design#is#required#for#an#electroless#process,#and#while#such#
a# bath# is# thermodynamically# unstable,# it# can# be# controlled# via# catalysis# to# only#
deposit# on# the# substrate.# # Like# corrosion,# electroless# deposition# is# often# studied#
using# electrochemical# methods.# # Frequently,# specialty# chemical# companies# for#
electroplating#baths#may#also#develop#and#market#electroless#baths.#

-
1.3.!!!Electrochemical!Products-
# It# has# been# argued# that,# at# least# in# the# United# States,# there# are# more# career#
opportunities#in#the#chemical#and#related#industries#that#focus#on#“chemical#products”#
rather#than#commodity#chemicals.6##Chemical#products#can#include#specialty#chemicals#
and#materials,#as#well#as#devices#that#utilize#chemistry.##Such#arguments#also#apply#to#
technologies# that# are# based# on# electrochemistry.# # # While# the# conceptual# foundations#
required# for# a# career# in# chemical# products# or# in# commodity# chemicals# may# be#
comparable,# the# different# industries# can# be# shaped# by# dissimilar# economic# factors,#
affecting#very#much#the#style#in#which#one#works.#
For# example,# an# engineer# working# to# produce# a# chemical# commodity# such# as#
chlorine#gas#of#a#specified#purity#may#design#to#minimize#operational#costs,#subject#to#
safety#and#environmental#constraints.##A#design#engineer#may#have#very#little#need#to#
interact# with# customers# or# the# company’s# marketing# division.# # In# contrast,# a#
manufacturer#of#a#chemical#product#may#obtain#competitive#advantages#by#producing,#
for#example,#an#electroplating#bath#that#imparts#superior#deposited;film#properties#to#
satisfy# a# market# niche.# # Since# each# application# can# have# different# needs,# the# engineer#
may# work# extensively# with# customers.# # For# an# electrochemical# product,# economic#
drivers,# such# as# time# to# market,# may# play# a# greater# role# in# commercial# success# than#
cost.##

10#
 To# further# expand# on# the# example# discussed# in# section# 1.1,# consider# a# highly#
specialized# plating# bath# used# in# semiconductor# manufacturing.# # A# standard# academic#
treatment# of# Cu# electrodeposition# describes# the# mechanism# of# the# two;step# electron#
transfer#process,#and#this#knowledge#is#a#valuable#starting#point.#However,#electrolytes#
contain# additives# that# have# historically# received# scant# attention# from# the# academic#
community,# although# they# may# be# the# difference# between# success# and# failure.# # Often#
these#additives#are#dismissed#as#being#part#of#an#empirical,#somehow#unscientific#art#of#
plating.#####
# However,# it# is# not# an# exaggeration# to# state# that# these# additives# are# a# key# to#
success#in#the#plating;chemistry#business.##After#all,#the#major#ingredients,#sulfuric#acid,#
cupric# sulfate# and# water,# are# commodities.# The# additives# are# the# key# intellectual#
property# (protected# as# a# trade# secret# or# through# patents)# that# distinguishes# one#
company’s# product# from# another.# # # In# some# cases,# multiple# companies# use# the# same#
additives,#and#care#is#taken#to#protect#the#precise#concentration#used#in#the#product.###
# Commercial# success# is# driven# by# factors# such# as# the# ability# to# plate# surface#
features#of#a#certain#size,#additive#controllability,#and#customer#service.##Furthermore,#a#
single# product# is# unlikely# to# satisfy# both# highly# automated,# high;tech# manufacturers#
that# operate# 24/7# using# fully# optimized# plating# tools# and# small# manufacturers# that#
process#a#range#of#products.##
# Specialty#batteries#are#another#electrochemical#product.#They#may#be#tailored#
to#satisfy#the#needs#of#particular#customers#(such#as#the#military#or#a#manufacturer#of#a#
laptop#computer)#or#markets.##Of#course,#some#batteries#such#as#alkaline#batteries#may#
be#considered#commodities#since#they#are#available#in#nearly#any#grocery#store#and#an#
average#customer#may#not#be#aware#of#any#real#differences#between#brands,#other#than#
their# appearance,# cost# and# advertisement# strategy.# # Some# products# clearly# grow# to#
become#commodities,#and#as#they#mature,#employment#opportunities#change.#
#
Note:! ! # Multiple# batteries# are# available# for# commercial# and# military# applications#
because# different# markets# can# have# different# needs# in# terms# of# performance# and#
cost.# # Primary#batteries,# such# as# an# alkaline# battery,# are# purchased# and# discarded#
after#a#single#use.##Secondary#batteries,#such#a#Li;ion#battery,#are#rechargeable,#and#
the# number# of# times# they# can# be# recharged# without# significant# performance#
deterioration#is#a#key#factor#for#commercial#success.#

# Strips# used# in# monitoring# glucose# levels# in# blood# are# another# electrochemical#
product.# # These# disposable# strips# are# used# in# a# device# that# contains# electronics# for#
measurement# of# electrochemical# response,# as# well# as# a# means# to# extract# the# blood#
sample.##We#generally#consider#that#a#device#can#also#be#an#electrochemical#product.##An#
obvious# example# is# a# fuel# cell,# and# not# only# size# but# possibly# also# the# type# of# fuel# cell#
will#depend#on#market#niche.##
# Returning#again#to#the#Cu#deposition#example#for#the#semiconductor#industry,#
the#plating#reactor#used#for#deposition#is#usually#designed,#manufactured,#and#serviced#
by# specialized# equipment# suppliers.# # These# reactors,# known# in# industry# parlance# as#
plating# tools,# are# an# electrochemical# product,# containing# an# electrochemical# cell,#
chemical# handling# apparatus,# and# automated# wafer# handling# capability.# # A# key#
consideration# for# design# of# the# electrochemical# cell# is# to# achieve# a# uniform# current#
distribution# (i.e.,# the# spatial# variation# in# reaction# rate),# while# ensuring# a# sufficient#
throughput.##

11#
Chapter#1.##Introduction#to#Electrochemistry#and#Electrochemical#Products#

# As# for# success# with# commercializing# additive# chemistry,# process# yield# is# a#
critical#factor#for#a#plating#tool.###The#maximum#usage#of#available#area#of#the#wafer#may#
also#be#crucial#if#the#tool#makes#electrical#contact#with#a#wafer#on#the#front#side#near#the#
edge.# # In# such# cases,# it# is# essential# that# the# contact# be# as# small# as# possible# without#
lowering# the# process# yield.# # As# for# other# products,# a# key# to# commercial# success# is# the#
time# to# market# because# of# the# massive# costs# of# qualifying# tools# (and# chemistries)# for#
use# in# semiconductor# manufacturing.# # Once# qualified,# it# may# be# challenging# for#
competing#plating#tools#to#overcome#this#initial#advantage.#
A# career# at# such# an# equipment# manufacturer# may# result# in# working# closely#
with#customers.#Close#cooperation#with#chemistry#vendors,#who#provide# the#specialty#
plating# additives# for# use# in# the# plating# tool,# and# metrology# companies,# who# provide#
tools#to#characterize#and#control#the#process,#is#also#common.#
!
1.4.!!Summary!
• Electrochemical# systems# involve# charge;transfer# reactions# that# occur# at# the#
interface# between# an# ionically# conducting# phase# and# an# electronically#
conducting#phase.###
• An# electrochemical# cell# requires# an# anode,# where# oxidation# reactions# tend# to#
occur#and#a#cathode,#where#reduction#happens.####
• The# rates# of# electrode# reactions# depend# not# only# the# intrinsic# kinetics# of# the#
charge#transfer#process#but#also#on#transport#processes.###
• Treatment# of# thermodynamics,# kinetics,# and# mass# transfer# requires# a#
consideration# of# the# response# of# charged# species# to# the# electrical# fields# that#
result# from# carrying# out# electrochemical# reactions# on# spatially# separated#
surfaces.#
• Design# of# an# electrochemical# process# or# product# is# aided# by# a# fundamental#
understanding# of# transport# phenomena,# electrode# kinetics,# and#
thermodynamics.#
• Career#opportunities#depend#on#the#maturity#of#a#technology,#and,#most#of#our#
former# students# and# colleagues# work# with# or# develop# electrochemical#
products,#such#as#novel#new#sensors,#new#batteries,#or#specialized#electrolytes#
or#electrodes.###
!
1.5.!!List!of!Symbols!
# iavg# # average#current#density,#A#cm;2#
# ilim# # limiting#current#density,#A#cm;2#
! r- - radial#position#along#a#wafer#or#RDE,#cm#
# r o# # radius#of#wafer#of#RDE,#cm#
#
!

12#
1.6.!!!Problems#

Almost-all-the-problems-in-this-section-may-require-extensive-research-on-the-Internet.--In-
addition,-you-also-may-need-to-estimate-certain-market-values.--

1.1##You#are#responsible#for#a#plating#Cu#onto#300;mm#wafers.###The#wafers#contain#the#
most# advanced# logic# chips# for# personal# computers.# # In# order# to# make# the# integrated#
circuits,# the# wafers# have# been# through# a# few# hundred# processing# steps,# and# you# are#
plating# the# final# metallization# layers.# # You# are# responsible# to# ensure# that# the# plating#
operation#is#functioning#with#a#very#high#yield#(and#realize#that#you#must#immerse#the#
wafer#in#a#bath#containing#sulfuric#acid#and#cupric#sulfate).-
#a.##What#is#the#final#value#of#the#wafer,#assuming#that#the#wafer#can#be#diced#
into# multiple# chips?# # Using# reasonable# numbers# for# the# size# of# the# chip,# you#
must#estimate#the#numbers#of#chips/wafer.##You#can#search#for#today’s#market#
value#of#logic#chips.###
b.# # Assuming# that# one# wafer# can# be# processed# every# five# minutes,# and# the#
plating# tool# operates# 24# hours# a# day,# what# is# the# total# gross# value# of# wafers#
produced#in#a#year?##Discuss#whether#these#numbers#are#reasonable#in#terms#of#
the#global#market#of#computer#chips#and#the#cost#of#building#a#manufacturing#
facility.# # Multiple# assumptions# will# be# required,# and# they# should# all# be# stated#
and#justified.#
#
#
1.2.##Fuel#cells#are#an#attractive#technology#as#a#means#of#direct#conversion#of#chemical#
energy#in#the#fuel#to#electrical#work.##There#are#multiple#environmental#advantages#to#
using# a# fuel# cell,# and# they# have# received# significant# interest# for# automotive# and#
residential;power# applications,# as# well# as# for# replacements# for# batteries# for# portable#
electronics,#such#as#a#laptop.###
a.# # Provide# estimates# for# power# requirements# for# each# of# these# applications,#
citing#all#references.#
b.###Estimate#target#costs#that#would#allow#for#penetration#of#fuel#cells#into#each#
of#these#markets,#assuming#technological#constraints#are#satisfied.##Justify#your#
numbers.#
c.# # Discuss# advantages# and# disadvantages# of# fuel# cells# over# competing#
technologies.#
#
#
1.3.##Because#of#its#electrical,#corrosion,#and#mechanical#properties,#gold#is#a#desirable#
metal#for#electrical#connectors#that#slide#into#another#part#(for#example,#a#circuit#board#
that#slides#into#another#board).##Assume#a#25;pin#connector,#which#is#to#be#plugged#into#
the#female#counterpart#shown#in#figure#1.5,#where#each#pin#is#perhaps#6;mm#tall,#upon#
which#gold#is#plated#on#4#mm#of#its#length.##The#pins#have#a#1;mm#diameter.##If#a#one;
micron# thick# layer# of# gold# is# required,# what# is# the# cost# of# gold# in# a# connector,# using#
today’s#cost#of#gold.##Likewise,#using#today’s#cost#of#gold,#provide#the#cost#per#liter#of#the#
gold# electrolyte,# assuming# a# gold# concentration# of# 40# mM.# Explain# why# a# supporting#
electrolyte# may# be# used# instead# of# additional# gold# salt# to# improve# electrolyte#

13#
Chapter#1.##Introduction#to#Electrochemistry#and#Electrochemical#Products#

conductivity.#
#
#
#

#
Figure!1.5.##Schematic#diagram#of#the#female#end#of#a#25;pin#connector.##The#pins#
on#the#male#end#of#the#connectors#are#plated#with#gold#of#a#thickness#~#1.0#µm.#
#
#
1.4.##Batteries#and#fuel#cells#are#both#electrochemical#devices#that#can#provide#electrical#
power# on# demand.# # Explain# the# key# differences# and# similarities# between# the#
technologies.##Use#the#Internet#and#any#available#literature#as#references.#
#
#
1.5.# # There# have# been# at# least# two# generations# of# glucose# sensors# that# have# been#
commercialized#for#care#of#diabetics.##Research#and#explain#the#principle#by#which#the#
electrochemical#measurement#is#made.##Further,#discuss#the#number#of#diabetics#in#the#
U.S.#and#the#number#of#times#per#day#a#patient#may#need#to#measure#his#or#her#glucose#
level.###
#
#
1.6.##Batteries#are#often#characterized#in#terms#of#energy#density#and#power#density#on#
a# per# volume# or# per# weight# basis.# # Explain# through# examples# when# an# application#
would# need# a# high# energy# density# and# when# a# high# power# density.# # # The# desire# to#
improve# energy# density# must# be# realized# through# safe# designs,# and# safety# is# always# a#
key# consideration.# # Besides# safety# and# cost,# what# are# other# important# factors# in#
designing#for#a#battery?###
#
#
1.7.# In# the# year# 2000,# the# global# production# of# aluminum# was# approximately# 1011#
pounds/year#(not#counting#recycled#Al).##An#electrochemical#process#using#a#molten#salt#
electrolyte#is#used#for#this#production,#and#its#overall#cell#reaction#can#be#written#as:#

Al O +!3/2!C→ 2!Al!+!3/2!CO2 # #
! 2 3
Assuming# that# the# cell# potential# is# approximately# 5V,# calculate# the# annual# electrical;
power# (total# current# ×# cell# voltage)# requirements# for# Al# production.# # For# this#
calculation,# you# may# need# to# review# Faraday’s# law# (chapter# 2).# # How# does# this# power#
consumption#compare#to#total,#global#electrical;power#production#and#to#the#capacity#of#
a#large#power#plant?#
#

14#
1.8.#Give#the#two#electrochemical#reactions#for#each#cell,#as#well#as#the#overall#reaction.##
It#is#important#to#balance#the#number#of#electrons#in#the#two#electrochemical#reactions#
to#get#the#correct#overall#reaction.##
a.##Cu(s)|#0.001#M#CuSO4(aq)||#0.1#M#CuSO4(aq)|Cu(s)#
b.#Ag(s)|AgCl(s)|HCl(aq)|H2(g)|Pt(s)#
c.##Zn(s)|ZnO(s)|KOH(aq)|O2(g)|Pt(s)#
d.###Pt(s)|O2(g)|NaOH(aq)||NH3(aq),NaNO2(aq)|Pt(s)#
e.## Pt(s)|FeCl2(aq),FeCl3(aq)||SnCl2(aq),SnCl4(aq)|Pt(s)#
#
#
1.9.##Another#very#common#electrochemical#device#is#a#pH#meter#and#the#pH#electrode.##
Explain#how#the#pH#electrode#works.#
#
#
1.10.# # # Renewable# electric;power# sources# such# as# solar# and# wind# energy# are#
environmentally# attractive.# # When# implemented# on# a# large# scale,# the# intermittent#
nature# of# these# sources# may# require# large;scale# storage.# # Multiple# storage# options# are#
possible,#depending#on#many#constraints#such#as#the#location#of#the#power#plant.##One#
approach#to#consider#is#to#use#batteries.###
a. Research# a# typical# size# of# a# power# plant,# and# estimate# the# energy;storage#
requirement# for# a# system# of# batteries.# # Compare# this# value# to# the# largest#
battery#systems#that#have#been#implemented#
b. Flow# batteries# have# been# considered# for# large;scale# storage# applications.##
Provide#examples#of#flow#batteries,#and#describe#how#they#work.#
c. What#are#the#possible#advantages#and#disadvantages#to#a#flow#battery?#
#
#
1.11.###Assume#you#are#designing#a#battery#that#is#expected#to#deliver#60#watts#of#power#
for#a#period#of#8#hours.##The#operational#cell#voltage#is#3.0#volts,#and#the#current#density#
(based#on#the#cross;sectional#area#of#the#battery#is#100#mA#cm;2.##Given#that#power#is#IV,#
what# should# be# the# cross;sectional# area# of# the# battery?# # Design# of# a# battery# may# in#
reality# involve# very# complex# optimization# to# achieve# high# peak# power# and# to# ensure#
utilization#of#all#of#the#active#material.##For#the#present#estimate,#assume#that#the#molar#
amounts#of#anode#and#cathode#material#are#equal#(each#reaction#involves#transfer#of#a#
single# electron)#and# the# average# molar# volume# is# 10# cm3/mol.# # # # What# is# the# required#
volume#of#active#material#to#achieve#the#design#goal?#

15#
 Chapter#1.##Introduction#to#Electrochemistry#and#Electrochemical#Products#

1.7.!!References!

!
1.# F.#A.#Trumbore,#D.#R.#Turner#and#Electrochemical#Society.,#The-Electrochemical-
Society- 1902D2002- :- A- Centennial- History,# Electrochemical# Society,# Pennington,# N.J.#
(2002).#
2.# G.# Prentice,# Electrochemical- Engineering- Principles,# Prentice# Hall,# Englewood#
Cliffs,#N.J.#(1991).#
3.# J.#D.#Jackson,#Classical-Electrodynamics,#Wiley,#New#York#(1999).#
4.# M.# M.# Denn,#Chemical- Engineering- :- A- New- Introduction,# Cambridge# University#
Press,#Cambridge#;#New#York#(2011).#
5.# A.# J.# Bard# and# L.# R.# Faulkner,# Electrochemical- Methods- :- Fundamentals- and-
Applications,#Wiley,#New#York#(2001).#
6.# E.# L.# Cussler# and# G.# D.# Moggridge,# Chemical- Product- Design,# Cambridge#
University#Press,#Cambridge#;#New#York#(2011).#
#
#
#

16#