Chapter 8: Measurement Of Small Signals; Overview; Measurement System Model And Physical Limitations - Gamry Reference 600+ Operator's Manual

Potentiostat/galvanostat/zra
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Chapter 8: Measurement of Small Signals

Overview

The Reference 600+ is a very sensitive scientific instrument. It can theoretically resolve current changes as
small as 1 femtoampere (1 × 10
about 6000 electrons per second!
The small currents measured by the Reference 600+ place demands on the instrument, the cell, the cables
and the experimenter. Many of the techniques used in higher current electrochemistry must be modified
when used to measure pA currents. In many cases, the basic physics of the measurement must be
considered.
This chapter discusses the limiting factors controlling low-current measurements. It includes hints on cell
and system design. The emphasis is on EIS (Electrochemical Impedance Spectroscopy), a highly demanding
application for the Reference 600+.

Measurement System Model and Physical Limitations

To get a feel for the physical limits implied by very sensitive current measurements, consider the equivalent
circuit shown in Figure 8-1. We are attempting to measure the cell impedance given by Z
This model is valid for analysis purposes even though the real Reference 600+ circuit topology differs
significantly.
In Figure 8-1:
E
ideal signal source
S
Z
unknown cell impedance
cell
I
"real" cell current
cell
R
current measurement circuit's current-measurement resistance
m
R
unwanted resistance across the cell
shunt
unwanted capacitance across the cell
C
shunt
C
current-measurement circuit's stray input capacitance
in
R
current-measurement circuit's stray input resistance
in
I
measurement circuit's input current
in
In the ideal current-measurement circuit, R
flows through R
.
m
With an ideal cell and voltage source, R
current measurement circuit is due to Z
The voltage developed across R
Kirchoff's and Ohm's laws to calculate Z
Z
= E
cell
A). To place this current in perspective, 1 fA represents the flow of
–15
is infinite while C
in
is infinite and C
shunt
.
cell
is measured by the meter as V
m
:
cell
× R
/ V
S
m
m
and I
are zero. All of the cell current, I
in
in
is zero. All the current flowing into the
shunt
. Given the idealities discussed above, use
m
57
.
cell
,
cel

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