Fundamentals of

Electrochemistry
CHEM*7234 / CHEM 720
Lecture 4
INSTRUMENTATION

OHM'S LAW
Ohms law, or more correctly called
Ohm's Law, named after Mr. Georg Ohm,
German mathematician and physicist
(b. 1789 - d. 1854), defines the
relationship between voltage, current
and resistance.

Where:
V = Voltage
I = Current
R = Resistance

or

V=IR
V/I = R

Example:

I=?
V=I*R
[]

I=V/R
I = 0.5 [A]

I = 9 [V] / 18

Series connection
I = I 1 = I 2 = I3
Vtotal = V1 + V1 + V3
Since V = I R, then
I3R3

Vtotal = I1R1 + I2R2 +

and
V
= I Rtotal
Setting both equationstotal
equal, we
get:
I3R3

I Rtotal = I1R1 + I2R2 +

We know that the current through each resistor (from the first
equation) is just I.
so

Rtotal = R1 + R2 + R3

I Rtotal = I(R1 + R2 + R3)

Parallel connection
Kirchhoffs Current Law states that
Itotal = I1 + I2 + I3
from Ohms Law
Itotal = V1/R1 + V2/R2 + V3/R3
but V1 = V2 = V3 = V
and Itotal = V/Rtotal
gives us:

1
1
1
1

Rtotal
R1 R2 R3

Capacitors
Vc

qc 1
i dt
C C

if
i imax sin(t)
where 2f
then
1
Vc imax sin (t) dt
C

imax sin(t - )
C
2

1
Xc imax sin(t - ) where Xc
2
C

where:
Vc voltage across the
capacitor
qc charge stored
C capacitance

Vc = Xc Imax (sint - /2)

Vc max = XC.Imax

there is 90 difference in phase

between current and voltage
Xc is called capacitive reactance
Xc = 1/(C) = 1/(2fC)
Xc a frequency dependent resistor

Impedance, resistance and

reactance
Impedance, Z, is the general name we give to the
ratio of voltage to current.

Resistance, R, is a special case of impedance

where voltage and current are NOT phase shifted
relative to each other.

Reactance, Xc, is an another special case in which

the voltage and current are out of phase by 90

Generalized Ohms Law

V=IZ

RC circuit

Because of the 90 phase shift between VC and VR

the resistance and capacitive reactance add
according to vector addition !!!
so

Z2RC = R2 + XC2

ZRC R XC
2

Low Pass Filter

Vin = ZRC I
and
Vout = XC I

XC
Vout Vin
ZRC

ZRC R XC
2

1
XC
2fC

Vout Vin

f
XC
Z

small
large
XC
Vout Vin

XC
R XC
2

f
XC

large
small
XC/Z small
Vout 0

For LPF with

R = 10 k and C = 0.1 F

Vout/ Vin 1.0

0.8

0.6

0.4

0.2

0.0
1

10

100

Frequency / Hz

1000

10000

High Pass Filter

Vin = ZRC I
and
Vout = R I

R
Vout Vin
ZRC

ZRC R XC
2

1
XC
2fC

Vout Vin

f
XC
Z

small
large
XC
Vout 0

R
R XC
2

f
XC
Z

large
small
R
Vout Vin

For HPF with

R = 10 k and C = 0.1 F

Vout/ Vin 1.0

0.8

0.6

0.4

0.2

0.0
1

10

100

Frequency / Hz

1000

10000

Band Pass Filter

Cascade an LPF and a HPF and you get BPF

In practice use Operational Amplifiers to construct

a BPF

Why RC circuits?

RC series creates filters

electrochemical cell may be simplified with
RC circuit (recall from lecture 2)

or, if faradaic process

present:

http://www.phy.ntnu.edu.tw/java/rc/rc.html

Operational Amplifiers (Op-amps)

What are they and why
do we need them ?

- very high DC (and to a lesser extent AC) gain amplifiers

- proper design of circuits containing Op-amps allows electronic algebraic
arithmetic to be performed as well as many more useful applications.
- they are essential components of modern-day equipment including your
POTENTIOSTAT / GALVANOSTAT !!

General Characteristics

very high input gain (104 to 106)

has high unity gain bandwidth
two inputs and one output
very high input impedance (109 to 1014 )
GOLDEN RULE #1 : an Op-amp draws no appreciable
current into its input terminals.

General Response
Electronically

speaking, the
output will do whatever is
necessary to make the
voltage difference between
the inputs zero !!
GOLDEN RULE #2

+ 15 V
I
N
P

T
S

OUTPU
T

- 15 V

In op-amps (as in life) you never get anything for free.

The gain () is achieved by using power from a power
supply (usually 15V). Thus the output of your op-amp
can never exceed the power supply voltage !

Ideal Op-Amp Behaviour

1.0

0.5

0.0

1.0

0.5

Signal

0.0

-0.5

-1.0

100

200

300

400

time

-0.5

-1.0

-50

1.0

0.5

0.0

-0.5

-1.0

100

200

time

300

400

50

100

150

200

250

300

350

400

time

1.0

0.5

Signal

Signal

infinite gain ( = )
Rin =
Rout = 0
Bandwidth =
The + and terminals have nothing to do with polarity they
simply indicate the phase relationship between the input and
output signals.

Signal

0.0

-0.5

-1.0

100

200

time

300

400

Open - loop Configuration

V0

Even if + - - 0 then Vo is very large because

is so large (ca. 106)
Therefore an open-loop configuration is NOT VERY
USEFUL.

Close-loop Configuration
Often it is desirable to return a fraction of the output
signal from an operational amplifier back to the
input terminal. This fractional signal is termed
feedback.
Rf
Vin

Rin
S

- + +

V0

Frequency Response of Op-Amps

The op-amp doesnt respond to all frequencies equally.

Voltage Follower

Vin

V0

Vo = V in

Why would this be of any use ?

Allows you to measure a voltage without

drawing any current almost completely
eliminates loading errors.

Current Amplifiers
Rf
Iin

Vo = - Iin Rf

V0

Summing Amplifiers

Rf

V1

R1

V2

R2

V3

R3

V1 V2 V3
Vo - Rf

R1 R 2 R3

V0

Integrating Amplifier
C
R
Vi

1
Vo Vi dt

RC
And if you wanted to integrate
currents ?

V0

A Simple Galvanostat

A Simple Potentiostat

A Real Potentiostat

The design of electrochemical

experiments
Equilibrium

techniques

potentiometry, amperometry differential

capacitance

Steady

state techniques

voltammetry, polarography, coulometry and

rotating electrodes

Transient

techniques

chronoamperometry, chronocoulometry,
chronopotentiometry

In all experiments, precise control or measurements

of potential, charge and/or current is an essential
requirement of the experiment.

The design of electrochemical

cell

Electrodes
working electrode(s),
counter electrode and
reference electrode

Electrolyte
Cell container

Working electrode

most common is a small sphere, small

disc or a short wire, but it could also be
metal foil, a single crystal of metal or
semiconductor or evaporated thin film
has to have useful working potential
range
can be large or small usually < 0.25
cm2
smooth with well defined geometry for
even current and potential distribution

Working electrode examples

mercury and amalgam electrodes

reproducible homogeneous surface,
large hydrogen overvoltage.

wide range of solid materials most

common are inert solid electrodes
like gold, platinum, glassy carbon.
reproducible pretreatment procedure,
proper mounting

Counter electrodes

to supply the current required by the W.E.

without limiting the measured response.
current should flow readily without the need
for a large overpotential.
products of the C.E. reaction should not
interfere with the reaction being studied.
it should have a large area compared to the
W.E. and should ensure equipotentiality of
the W.E.

Reference electrode
The role of the R.E. is to provide a fixed
potential which does not vary during
the experiment.
A good R.E. should be able to maintain
a constant potential even if a few
microamps are passed through its
surface.

Micropolarisation tests

(a) response of a good and (b) bad reference

electrode.

Reference electrodes examples

mercury mercurous chloride (calomel)

the most popular R.E. in aq. solutions; usually
made up in saturated KCl solution (SCE);
may require separate compartment if
chloride ions must be kept out of W.E.

silver silver halide

gives very stable potential; easy to prepare;
may be used in non aqueous solutions

The electrolyte solution

it consists of solvent and a high concentration

of an ionised salt and electroactive species
to increase the conductivity of the solution, to
reduce the resistance between

W.E. and C.E. (to help maintain a uniform current

and potential distribution)
and between W.E. and R.E. to minimize the
potential error due to the uncompensated solution
resistance iRu

Troubleshooting

is there any response?

is the response incorrect or erratic?
is the response basically correct but
noisy?

For resistor as a dummy

cell:
W.E.

C.E. + R.E.

Cyclic Voltammogram
2.2 0 0 E +0
2.0 0 0 E +0
1.8 0 0 E +0
1.6 0 0 E +0
1.4 0 0 E +0
1.2 0 0 E +0
1.0 0 0 E +0
8 .0 0 0E -1
6 .0 0 0E -1
4 .0 0 0E -1
2 .0 0 0E -1
-2 .7 7 6E -1 6
-2.0 00 E -1
-4.0 00 E -1
-6.0 00 E -1
-8.0 00 E -1
-1 .0 0 0E +0
-1 .2 0 0E +0
-1 .4 0 0E +0
-1 .6 0 0E +0
-1 .8 0 0E +0
-2 .0 0 0E +0
-0 .3 0 0

-0 .2 5 0

-0 .20 0

-0 .15 0

-0 .10 0

-0 .0 5 0

0 .0 00

E / V vs R E

0 .05 0

0 .1 0 0

0 .1 5 0

0 .2 0 0

0 .25 0

0 .3 0 0

For RC as a dummy cell (with some filtering in pot.):

W.E.
C.E. + R.E.
Cyclic Voltammogram
2 .5 0 0 E -1
2 .2 5 0 E -1
2 .0 0 0 E -1
1 .7 5 0 E -1
1 .5 0 0 E -1
1 .2 5 0 E -1
1 .0 0 0 E -1
7 .5 0 0 E -2
5 .0 0 0 E -2
2 .5 0 0 E -2
-3 .4 6 9 E -1 7
-2 .5 0 0 E -2
-5 .0 0 0 E -2
-7 .5 0 0 E -2
-1 .0 0 0 E -1
-1 .2 5 0 E -1
-1 .5 0 0 E -1
-1 .7 5 0 E -1
-2 .0 0 0 E -1
-2 .2 5 0 E -1
-2 .5 0 0 E -1
-0 .3 0 0

-0 .2 5 0

-0 .2 0 0

-0 .1 5 0

-0 .1 0 0

-0 .0 5 0

0 .0 0 0

E / V vs R E

0 .0 5 0

0 .1 0 0

0 .1 5 0

0 .2 0 0

0 .2 5 0

0 .3 0 0

For RC as a dummy cell (without any filtering in pot.):

Cyclic Voltammogram
3 .0 00 E +0

2 .5 00 E +0

2 .0 00 E +0

1 .5 00 E +0

1 .0 00 E +0

5 .0 0 0 E -1

0 .0 00 E +0

-5 .0 00 E -1

-1 .0 0 0 E +0

-1 .5 0 0 E +0

-2 .0 0 0 E +0

-2 .5 0 0 E +0

-3 .0 0 0 E +0
-0 .2 2 5 -0 .2 0 0

-0 .1 5 0

-0 .1 0 0

-0 .0 5 0

0 .0 0 0

E / V vs R E

0 .0 5 0

0 .1 0 0

0 .1 5 0

0 .2 0 0 0 .2 2 5