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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

V=I·R
or
V/I = R
Example:

I=?
V=I*R I=V/R I = 9 [V] / 18 [Ω]
I = 0.5 [A]
Series connection
I = I1 = I2 = I3

Vtotal = V1 + V1 + V3

Since V = I R, then Vtotal = I1R1 + I2R2 + I3R3

and Vtotal = I Rtotal

Setting both equations equal, we get: I Rtotal = I1R1 + I2R2 + I3R3

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

I Rtotal = I(R1 + R2 + R3) Rtotal = R1 + R2 + R3


Parallel connection
Kirchhoff’s Current Law states that
Itotal = I1 + I2 + I3
from Ohm’s 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
qc 1
Vc    i dt where:
C C
if Vc – voltage across the
i  imax  sin( ωt) where ω  2f
capacitor
then qc – charge stored
1
Vc   imax  sin (ωt) dt C – capacitance
C
1 π
 imax  sin( ωt - )
ωC 2
 1
 Xc  imax  sin( t - ) where Xc 
2 C
Vc = Xc · Imax (sint - /2)
Vc max = XC.Imax

 there is 90º difference in phase between


current and voltage
 Xc is called capacitive reactance
 Xc = 1/(C) = 1/(2fC)
 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 Ohm’s Law


V=I·Z
RC circuit

Because of the 90º phase shift between VC and VR the


resistance and capacitive reactance add according to
vector addition !!!
so Z2RC = R2 + XC2

ZRC  R  XC 2 2
Low Pass Filter
Vin = ZRC· I
and
Vout = XC · I

XC 1
Vout  Vin ZRC  R  XC
2 2
XC 
ZRC 2fC
XC
Vout  Vin
R 2  XC 2

f  small f  large
XC  large XC  small
Z  XC XC/Z  small

Vout  Vin Vout  0


For LPF with R = 10 k and C = 0.1 µF

Vout/ Vin 1.0

0.8

0.6

0.4

0.2

0.0

1 10 100 1000 10000


Frequency / Hz
High Pass Filter
Vin = ZRC· I
and
Vout = R · I

R 1
Vout  Vin ZRC  R  XC
2 2
XC 
ZRC 2fC
R
Vout  Vin
R 2  XC 2

f  small f  large
XC  large XC  small
Z  XC Z  R

Vout  0 Vout  Vin


For HPF with R = 10 k and C = 0.1 µF

Vout/ Vin 1.0

0.8

0.6

0.4

0.2

0.0

1 10 100 1000 10000


Frequency / Hz
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
Electronicallyspeaking, the
output will do whatever is
necessary to make the voltage
difference between the inputs
zero !!
GOLDEN RULE #2
+ 15 V
I
N - OUTPUT
P
U
T +
S
- 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
 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.

-
1.0
1.0

0.5
0.5
Signal

Signal
0.0
0.0

-0.5

+
-0.5

-1.0
-1.0

0 100 200 300 400


-50 0 50 100 150 200 250 300 350 400
time
time

-
1.0
1.0

0.5
0.5
Signal
Signal

0.0
0.0

+
-0.5
-0.5

-1.0
-1.0

0 100 200 300 400


0 100 200 300 400
time
time
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 - -
V0
S
+ +
Frequency Response of Op-Amps
The op-amp doesn’t respond to all frequencies equally.
Voltage Follower

- V0
Vin
+

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
- V0
+

Vo = - Iin Rf
Summing Amplifiers

V1 R1 Rf

V2 R2
- V0
V3 R3 +

 V1 V2 V3 
Vo  - Rf    
 R1 R2 R3 
Integrating Amplifier

R -
Vi V0
+

1
Vo  -
RC  Vi dt

And if you wanted to integrate currents ?


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?

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