1

Fall, 2000
Chemistry 382/378
Role-Playing Lab in
Instrumental Analysis
Experiment #05
Polarography

Prof. John P. Walters

Dep't. of Chemistry
St. Olaf College
Northfield, MN 55057
507-646-3429
walters@stolaf.edu

Perhaps the most fascinating thing about solution electrochemistry is the fact that you literally stick
one end of a wire into the solution you want to analyze, and connect the other end to your
electronics and computer. There hardly could be a more graphic illustration of the interfacing of
computers, electronics, and chemistry than this. Of course, the wire is not simply a wire. It must
have certain properties in the solution, such as resistance to attack and the ability to conduct
electricity.
Mercury Fill
Leveling Bulb

Aluminum
Plate
Tygon
Tubing

Tight Fit

Tri-Pod Stand

Tight Fit

Capillary
Cell

Solution

Mercury Drop

Epoxy Painted Shelf

Figure 1 An illustrative dropping mercury electrode.

Even more fascinating than the ensemble

of instruments collected to do
electrochemistry is one of the more
historical wires that is stuck into the
solution. This is the dropping mercury
electrode, an illustrative example of
which is shown here in Figure 1.
Mercury is placed in the leveling bulb at
the top of the tri-pod stand. The bulb is
held in an aluminum plate. A length of
tygon tubing is tightly fit to the bottom of
the bulb, and is dropped down into the
electrochemical cell. A short section of
capillary tubing is tightly fit into the
tygon. Because of the very small bore of
this tubing, mercury flows slowly
through it, forming a drop at the end that
detaches every few seconds when its
weight is greater than what the surface
tension will support.
Mercury is itself a fascinating metal. It
not only is an excellent conductor, it also
is a liquid at room temperature. And,
other metals dissolve in it to form
amalgams. The down side to using
mercury is its toxicity, which is severe if
inhaled, ingested, or absorbed through
the skin. Portions of the Fisher Scientific
MSDS on mercury follow, and should be
thoroughly read before any lab work is
contemplated. Take care of this now,
please
.

MERCURY HAZARDS IDENTIFICATION

EMERGENCY OVERVIEW
Appearance: Silvery, reflective liquid.
WARNING! CAUSES SKIN IRRITATION. MAY CAUSE ALLERGIC SKIN
REACTION. THIS SUBSTANCE HAS CAUSED ADVERSE REPRODUCTIVE AND
FETAL EFFECTS IN ANIMALS. MAY BE ABSORBED THROUGH THE SKIN.
CAUSES DIGESTIVE TRACT
IRRITATION. MAY CAUSE CENTRAL NERVOUS SYSTEM EFFECTS. MAY CAUSE
SEVERE EYE IRRITATION AND POSSIBLE INJURY. CAUSES SEVERE
RESPIRATORY TRACT IRRITATION. INHALATION OF FUMES MAY CAUSE
METAL-FUME FEVER.
Target Organs: Blood, central nervous system.
Potential Health Effects
Eye:
Contact with eyes may cause severe irritation, and possible eye burns. Vapors may cause
eye irritation.
Skin:
May cause skin irritation. May be absorbed through the skin in harmful amounts. May cause
skin sensitization, an allergic reaction, which becomes evident upon re-exposure to this
material.
Ingestion:
May cause gastrointestinal irritation with nausea, vomiting and diarrhea. May cause effects
similar to those for inhalation exposure.
Inhalation:
Causes respiratory tract irritation. Inhalation of fumes may cause metal fume fever, which is
characterized by flu-like symptoms with metallic taste, fever, chills, cough, weakness, chest
pain, muscle pain and increased white blood cell count. May cause central nervous system
effects including vertigo, anxiety, depression, muscle incoordination, and emotional
instability. May cause severe respiratory tract irritation.
Chronic:
Chronic exposure to mercury vapor may cause permanent central nervous system damage.
Early symptoms include weakness, fatigue, anorexia, loss of weight, and disturbances of
gastrointestinal function. Unintentional tremors of the fingers, eyelids, lips, and entire body
may occur at later stages. Behavioral and personality changes, increased excitability, loss of
memory, insomnia and depression may occur.

3
FIRST AID MEASURES
Eyes:
Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the
upper and lower lids. Get medical aid immediately.
Skin:
Get medical aid. Immediately flush skin with plenty of soap and water for at least 15
minutes while removing contaminated clothing and shoes.
Ingestion:
Never give anything by mouth to an unconscious person. Get medical aid immediately.
Wash mouth out with water.
Inhalation:
Remove from exposure to fresh air immediately. If not breathing, give artificial respiration.
If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician:
Treat symptomatically and supportively. The use of DMSA or BAL as antidotal treatment
should be determined only by qualified medical personnel (Medical Toxicology, 1988).
ACCIDENTAL RELEASE MEASURES
Spills/Leaks:
Vacuum or sweep up material and place into a suitable disposal container. Wear a self
contained breathing apparatus and appropriate Personal protection.
HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Use
with adequate ventilation. Minimize dust generation and accumulation. Avoid breathing
dust, vapor, mist, or gas. Avoid contact with eyes, skin, and clothing. Keep container
tightly closed. Avoid ingestion and inhalation.
Storage:
Store in a cool, dry, well-ventilated area away from incompatible substances. Keep away
from metals (such as wedding or engagement rings).
PRODUCT NAME:
MERCURY (METAL)
FORMULA:
HG
FORMULA WT:
200.59
CAS NO.:
07439-97-6
NIOSH/RTECS NO.: OV4550000

HEALTH
FLAMMABILITY
REACTIVITY
CONTACT

4
0
1
3

EXTREME (POISON)
NONE
SLIGHT
SEVERE (LIFE)

HAZARD RATINGS ARE 0 TO 4 (0 = NO HAZARD; 4 = EXTREME HAZARD).

4
Clearly, mercury is toxic. But, as long as there are no spills, as long as the whole electrode to
deliver the mercury to the solution has been constructed, assembled, and tested prior to the time you
have to use it, and provided there are safe methods available to you to fill and empty the cell
containing the solution into which the mercury flows, then the polarography experiment can be done
with only normal safe lab practices. That is the case here. When you come into this lab, you will
find two polarographic systems set up for you. You will have the opportunity to use them, and to
change the chemistry of the solutions being analyzed. But their assembly will have all been done for
you.
The Apparatus Pictured
The complete apparatus is pictured in Figure 2.
At the top of the apparatus is a leveling bulb
partially filled with mercury (Figure 3).

Figure 3 The mercury leveling bulb

Figure 2 The DME apparatus
Contact is made to the mercury by inserting a
copper wire into it. Over time, the mercury will show some
copper contamination, but for our uses here it will be
negligible.
Mercury flows out of the leveling bulb downward through
a length of tygon tubing into the cell that contains the DME
capillary. The tygon tubing filled with mercury and entering
the cell from above is visible in the center of Figure 4. The
three fingered clamp holds the top of the capillary tube,
which is inserted firmly up inside the larger tygon tubing.
Clearly, the tygon glass seal has to be firm and durable. It
is the stiction of tygon on glass that makes this so. Tygon
is, unfortunately, somewhat oxygen permeable.

Figure 4 Mercury into the DME

5
The bottom of the cell into which the DME is inserted
holds the solution being analyzed. This is shown in
Figure 5. Because the glass capillary and the glass cell
walls are equally clear, the DME as such is hard to see in
this picture.
There is a danger that in handling the solutions, the cell
parts (top and bottom) might become accidentally
separated. Since the bottom of the cell has a rather large
puddle of mercury in it after even a few hours of use, this
could be a disastrous happening. Thus, the cell parts are
firmly held together with a cam type of clamp, and the
cam is held in an engaged position by a plastic cable tie.
This means that the cell can only be filled and emptied by
a combination of syringe (to fill it) and vacuum aspirator
(to empty it). In this way, it is never necessary to take it
apart and come into any kind of contact with the mercury
it may contain.
Figure 5 The bottom of the DME cell
The vacuum pump that is used to aspirate out the contents
of the cell is shown in Figure 6. This pump pulls a vacuum
sufficient not only to draw the solution out of the cell into
the waste bottle (Figure 7), but also excess mercury that
accumulates over time in the bottom of the cell.

Figure 6 The cell aspiration pump

This means that the waste bottle forms a key
part of the mercury safe handling system. All
mercury that is in it is typically covered by a
layer of acidified water waste. The same is
true when the mercury is in the polarographic
cell. The leveling bulb is partially stoppered
at the top. Thus, mercury vapor is always
trapped in glass or under water, throughout
the whole apparatus.
Figure 7 The waste bottle for sample + Hg

6
Nitrogen is used to deaerate the solution. This is done by
first bubbling nitrogen through the solution (called
sparging) to displace the dissolved oxygen. After a short
time, most of the oxygen has been removed and replaced
with nitrogen, which produces no electrochemical signal.
After that, a flowing layer of nitrogen is directed over the top
of the solution to keep it from absorbing oxygen from the air.
A two pronged gas delivery tube is used to control the
nitrogen. It is shown in Figure 8. Two hoses come to it.
When nitrogen flows through the front hose, it is directed
down into the solution. When it flows through the back
hose, it is directed over the top of the solution.
The nitrogen pathway is selected with a small three way
toggle valve as shown in Figure 9.

Figure 8 The nitrogen inlet tubes

When the valve is one position, gas flows
through one tube. When in the other position,
gas flows through the other tube. Practice with
these valves is needed to master their use.
The toggle valves just switch the path of the
gas. Its flow rate is set by a needle valve
mounted on one of the legs of the tri-pod stand
as shown in Figure 10.
Typically, the toggle valve is first set to direct
Figure 9 A nitrogen toggle valve
the nitrogen down into the solution in the cell. During
this time, the needle valve is turned off. The needle valve
then is very carefully opened until a gentle stream of
bubbles is observed passing through the solution. This
starts the deaeration. It usually takes between 5 and 10
minutes to deaerate a solution. After this, the toggle
valve is switched to the position to direct the same gas
flow across the top of the solution. Once set, the needle
valve is not changed.
Figure 10 The needle valve

When the system is shut down after a days run, the

deaeration gas is turned off, the
solution is aspirated out of the cell, and a small amount of deionized water
is played over the DME capillary tip to rinse it. Then the DME is allowed to
drop for a few minutes. After that, the mercury flow is shut off by
tightening a pinch clamp on the tygon tubing so it completely restricts
mercury flow (see Figure 11). In this way, the DME is cleaned and will be
ready to run the next day. It is never stored under water or in any electrolyte
solution. Should it become plugged, it has to be discarded and a new one
placed in the tygon. This is an elaborate, and undesired, job.
Figure 11 Clamp

7
The DME apparatus is on a
cart, and the potentiostat is
placed in a plasticware box
on the back of the cart. A
digital voltmeter is used to
monitor the potentiostat input
and output voltages. A large
ribbon cable connects the 50
pin terminal block on the side
of the cart to a companion
Mac, 640AV computer
carrying LabVIEW and a
single NB-MIO-16L A/D
board. Solutions to be
analyzed are placed on a
small shelf at the front of the
cart. All of this is shown in
Figure 12.
This completes the
apparatus.
Figure 12 The potentiostat and computer interface cable
The Potentiostat
As shown in Figure 13,
the potentiostat is made
Voltage Follower
from 3 operational
with Gain
amplifiers. The top
amplifier receives the
+
Input from D/A
output from the D/A
9
Converter
converter as a voltage and
applies it to the counter
+ 9
electrode in the
Counter Electrode
electrochemical cell. The
Reference Electrode
Voltage Follower
reference electrode probes
+
Working Electrode
- 9
the voltage dropped
between the counter
electrode and the working
+ 9
electrode, picking off a
fraction of it close to the
Current Follower
working electrode. This
+
voltage is applied to the
- 9
second amplifier. The 2nd
Output to A/D
amplifier plus the
Converter
resistance between the
Figure 13 Basic 3 Electrode Potentiostat Circuit
counter electrode and the
reference electrode form
the feedback loop for the first amplifier. This sets the voltage applied to the working electrode to be
essentially the same as the output of the D/A converter, no matter what the solution or reference
electrode resistances are. Current in the working electrode is measured with the current follower, as
described on the next page.
+ 9

8
The key operating principle of the three
amplifier potentiostat shown in Figure 13 is the
virtual ground.

In Figure 14, we see that a current is the result

of a potential acting through a resistance. If one
end of the resistance is returned to the same
ground point to which the low potential point of
the battery is connected, then the current is
determined only by the size of E/R.

In the bottom of Figure 14, we see that a current

follower has as its input only a current,
i
generated in any way that happens to be
( )
appropriate. When the amplifier as such is
balanced, then the potentials at the inverting and
non-inverting inputs are very close to the same
+
value, whatever that value is. In a current
follower, the non-inverting in[put is physically
connected to ground. Thus, the inverting input
Figure 14 Virtual ground in a current follower is very close to zero potential, or it is virtually at
ground potential. We call this then a virtual
ground. A current into that point will be determined only by the effective potential that operates
through the effective resistance.
R

In the potentiostat, the potential is that applied by the voltage follower with gain to the working
electrode and reference electrode. The resistance is complex and depends on the diffusion that
occurs in solution. The current however, still is determined by just the applied potential and the
effective resistance. The current follower holds the potential of the working electrode at virtual
ground to ensure that this is so. This is illustrated in Figure 15 below.

D
C

NI NB-MIO-16L A/D,
D/A and DIO Board to
Output to Potentiostat
LabVIEW Potentiostat
Driver and Scan
Selection/Controls

Voltage
Follower
w/Gain

Current
Follower

CE RE WE

Electrochemical Cell

NI NB-MIO-16L A/D,
D/A and DIO Board to
Input from Potentiostat
LabVIEW Potentiostat
V/t, i/t, and i/V
Graphic Displays

Figure 15 The 3 amplifier potentiostat connected to the three electrode electrochemical cell

9
1

4
Reference Electrode

Reference Electrode

Reference Electrode

Reference Electrode

+
E

(0) -

Working Electrode Working Electrode Working Electrode Working Electrode

4
Reference Electrode

Reference Electrode
Reference Electrode
Reference Electrode

+
E
(0) -

E
-

E
-

E
-

Working Electrode Working Electrode Working Electrode Working Electrode

One of the most difficult things to

understand about how the potentiostat
works revolves around the
relationships between the magnitude
of a potential (a scalar) and the polarity
of an electrode (a vector). This is
diagrammed in Figure 16.
It is important to remember that the
electrochemistry in a cell depends on
the potential difference between two
electrodes, and the polarity of one
electrode relative to the other. The
magnitude of the potential difference
(E) applied between the reference
electrode and the working electrode is
shown to increase progressively in
four steps in both insets A and B of
Figure 16.
But, in inset A, we view the reference
electrode as becoming more positive.
In inset B, we view the working
electrode as becoming more negative.
In either case, the effect is the same.
As the potential difference between the
two electrodes increases, the reference
electrode becomes more positive
because the working electrode
becomes more negative.

Figure 16 The relation between magnitude and polarity

In the potentiostat, where the current

results from a potential difference
between the reference and working electrodes, the current follower holds the potential of the
working electrode at virtual ground, relative to the reference electrode. Thus, its measured potential
remains at approximately zero magnitude relative to the ground reference point from which the
reference electrode potential is also measured. But, its polarity will always be negative relative to the
reference electrode, simply because the voltage follower always drives the counter electrode positive
relative to that same ground. The voltage follower does this because it is wired that way.
In a word then, when the potentiostat voltage follower drives the counter electrode positive, and the
current follower holds the working electrode at virtual ground, the effect is the same as driving the
working electrode negative, and holding the counter electrode at ground. The potential difference
between the two electrodes will increase as the output of the voltage follower increases. This is
magnitude. But the polarity of the working electrode will remain negative.
When we use the LabVIEW potentiostat, we talk about scanning the potential of the working
electrode anodically (positive relative to the reference) or cathodically (negative relative to the
reference). When the potentiostat output becomes more positive, we scan cathodically. When it
becomes less positive, we scan anodically. In both cases, the potential of the working electrode
relative to ground remains constant, and very close the zero, as a virtual ground point. Setting an
initial anodic potential means setting the potentiostat output negative. This has the same effect as
setting the working electrode to a positive (anodic vs. the reference) voltage. Setting an initial
cathodic potential means setting the potentiostat output positive. This has the same effect as setting
the working electrode at a negative (cathodic vs. the reference) potential.

10
IN from
Working
Electrode
(DME)

IN from
Reference
Electrode
(SCE)

+9 vDC
Battery

OUT to
Counter
Electrode
(Pt)

Ground
Connector

+9 vDC Power Bus (red colored all connected)

In from D/A
Converter
Channel 0

8 7 6 5

8 7 6 5

8 7 6 5

2 3 4

2 3 4

2 3 4

Ground
Bus
(green
colored)

Ground
Connector

OUT to A/D
Converter
(Channel 0)

Ground
Connector
-9 vDC Power Bus (black colored all connected)

Battery
On-Off
Switch

-9 vDC
Battery

External Power Supply Input Jacks

(Disconnect internal batteries first!!!)

Modular PlugIn Feedback

Resistor

Figure 17 Wiring and connecting the plasticware potentiostat

The actual circuitry for the potentiostat is to be assembled within a plasticware box following the
circuit diagram shown in Figure 17.
Three type 741 operational amplifier chips are to be used. They should be placed in the
experimenters socket more or less as shown, paying particular attention to their orientation with
regard to the pin one dot.
The plasticware box has connections that have to be made to the polarograph and tri-pod electrode
stand. It will be up to you to identify the leads on the polarograph that connect to the SCE reference
electrode, the DME working electrode, and the platinum counter electrode. All of these connections
are shown as an electrical schematic in Figure 18, and also are shown as a pictorial diagram shown
as Figure 19 on the next two pages. When you have identified these cables and connectors, you will
need to connect them to the proper outputs of the Figure 17 potentiostat in the plasticware box.
Tutorial assistance likely will be needed, and will be available.
The D/A input and the A/D output of the potentiostat have to be connected to the 640AV Mac that
holds the NB-MIO-16 board and LabVIEW software. This is not difficult, but is best done with
some tutorial assistance. The connections needed are shown in Figure 20.

11
(+9 vDC)

(in)

(-)

8 7 6 5

2 3 4

(in)

(+)

(out)

(-9 vDC)
Pinouts for the type 741 Operational Amplifier

+ 9

Voltage Follower
with Gain

Input from D/A

Converter

+
- 9
+ 9

Counter Electrode
Reference Electrode

Voltage Follower

+
- 9

Working Electrode

+ 9
-

Current Follower
+
- 9
Output to A/D
Converter

Figure 18 Wiring the 741 operational amplifiers to make the potentiostat in the plasticware box.

12
+9 v
-

-9 v

D/A
ground

OUT to
Counter
Electrode
(Pt)

IN from D/A
Converter
(Channel 0)
IN from
Reference
Electrode
(SCE)

DME
+9 v
2

D/A
ground

SCE
Pt
6

-9 v
OUT to
Counter
Electrode
(Pt)

A/D
ground
IN from
Working
Electrode
(DME)

+9 v
2

7
4

-9 v

ground
OUT to A/D
Converter
(Channel 0)

A/D
ground

Figure 19 Physical layout of the connections between the potentiostat and the electrochemical cell.

A/D Channel 0
Input Twisted Pair

13
D/A Channel 0
Twisted Pair

System
Ground

2 4

10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50

11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49

Reference
Jumper - do not
remove

Drop
Knocker
Line

Vac.
Line

N2
Line

Digital
Ground

D/A Channel 1
Twisted Pair

Adc Input GrouND

Adc In CHannel 0
Adc In CHannel 1
Adc In CHannel 2
Adc In CHannel 3
Adc In CHannel 4
Adc In CHannel 5
Adc In CHannel 6
Adc In CHannel 7
Adc In SENSE Line
DAC channel 1 OUT
dAc Output GrouND
byte A DigIO bit 0
byte A DigIO bit 1
byte A DigIO bit 2
byte A DigIO bit 3
DIGital i/o GrouND
+5 V dc @ 500 mAmp
EXternal STROBE out
EXTernal GATE in
pulses SOURCE in 1
gate counted OUT 2
count GATE on in 2
pulses SOURCE in 5
gate counted OUT 5

1
3
5
7
9
11
13
15
17
19
21
23
25
27
29
31
33
35
37
39
41
43
45
47
49

2
4
6
8
10
12
14
16
18
20
22
24
26
28
30
32
34
36
38
40
42
44
46
48
50

Adc Input GrouND

Adc In CHannel 8
Adc In CHannel 9
Adc In CHannel 10
Adc In CHannel 11
Adc In CHannel 12
Adc In CHannel 13
Adc In CHannel 14
Adc In CHannel 15
DAC channel 0 OUT
EXTernal REFerence
DIGital i/o GrouND
byte B DigIO bit 0
byte B DigIO bit 1
byte B DigIO bit 2
byte B DigIO bit 3
+5 V dc @ 500 mAmp
SCANned CLocK out
EXTernal TRIGger in
EXTernal CONVert in
count GATE on in 1
pulses SOURCE in 2
gate counted OUT 2
count GATE on in 5
Freq. division OUT

A/D Channel 0
Input Twisted Pair

D/A Channel 0
Twisted Pair
Drop
Knocker Vacuum
Line
Line

N2
Line

Figure 20 NB-MIO-16L board and terminal block connections

Digital
Ground

System
Ground

14
The connections shown in Figure 20 are of three types. The A/D twisted pair receives the output of
the current follower in the potentiostat and carries it to the NB board as an input signal. The D/A
twisted pair carries the DAC-0 channel as an output to the potentiostat. These leads are color coded,
and can be easily traced between the connector and the potentiostat. This should be done prior to
using the apparatus.
The drop knocker, nitrogen gas on/off vale, and aspiration vacuum pump are all switched on or off
by solid state relays controlling the primary 110 vAC power to them. One set of solid state relays
used for this are shown in Figure 20. The digital lines from the NB board are then used as outputs
to turn on or off the solid state relays. This is an excellent way to control devices that draw
significant amounts of AC power.
When you are in the lab, trace the lines that run from the 50 pin terminal block to the devices shown
in Figures 20 and 21. You will have to stretch to do this, since the solid state relays are underneath
the cart that holds the polarograph. Also trace out the ribbon cable that connects the terminal block to
the NB board in the Mac 640AV computer. The rest of the work involves the LabVIEW software on
that computer, so it is important that you have a good physical picture of what is being controlled
before you start building the LabVIEW potentiostat controller.

110 vAC Power Cord

Circuit
Breaker
AC Line
Switch

Nitrogen Line
Switch 1
AC out

AC out
AC in
SSR 1
+

- black

+ red

Vacuum Pump
Switch 2

AC in

SSR 2
+

- black

Figure 21 Solid state relays used to control nitrogen valve and vacuum pump devices

+ red

15
The LabVIEW potentiostat is a VI that is best viewed in terms of how the DME is operated.
Consider the sequence portrayed in Figure 22 below.

1 Start Mercury Drop

Read Current
at DME vs. Ground

Detach Drop with

Drop Knocker

6 Apply Current to
Drop Knocker
Solenoid

2 Add Solution to Cell

Repeat Cycle

9 Until Done

Figure 22 Pictorial of DME sequence

Wait for Drop to

Grow to Desired Area

Set Potential
to Initial Value

Change Potential

16

The experiment starts when the pinch clamp on the mercury flow line to the capillary is opened and
the mercury drops start free falling (1). Then, solution is added to the cell (2), and the potential set
to the desired starting point (3). Time is then allowed to pass while the mercury drop grows to some
size less than what it would take to freely detach (4), when the current is read (5). After this, the
solenoid controlling the drop knocker is powered (6), and the drop knocker plunger taps the side of
the cell, causing the drop to fall off (7). The potential then is set to a new value (8), and the whole
cycle is repeated (9) for as many times as it takes to complete the experiment.
One of these cycles takes 2 to 3 seconds. The number of cycles used to record the data depends on
the size of the potential change between drops.
To better see the timing, refer to Figure 23
3 Read Current
for Drop #1

Read Current
for Drop #2

13

Area of Drop

14

2
Allow Drop #1 to
Grow for time t

12

Allow Drop #2 to
Grow for time t

Step Potential
Cathodic by E
E

Allow Drop #3 to
Grow for time t
10
Step Potential
Cathodic by E

Applied Potential

Detach Drop #3

Detach Drop #2

Detach Drop #1

1
Set Potential at E

Read Current
for Drop #3

6
E + E

Time
11
E + 2E
t

t
Time

Figure 23 Timing of DME sequence

When the potential is first set (1), it is held constant for a time t. This time is set by the time it takes
the drop to grow to some desired size (2). Before the drop is detached (4), the current must be read
(3), at least once for each drop.

17
To compensate for small variations in the surface geometry of the drop when it is large, several
thousand current readings are usually taken in a fraction of a second and averaged.
Then, after the drop has been detached, the potential is stepped by an amount E. This usually is a
small potential, so that there is a need for many drops to be repeated to scan the total voltage from 0
to -1.7 or so.

13

14

15

16

17

18

19 20

21

22

12
11

10
6

9
8

24

23
2

Figure 24 The front panel of the Potentiostat VI (numbered for explanation)

The whole potential scan can take several minutes, especially if the potential is scanned from 0 to 1.7 and back to 0, and the results overlaid to ensure reproducible electrode response. The solution
then is changed, and another scan done on a new solution.
All of the timing and reading shown in Figures 22 and 23 is done by the LabVIEW potentiostat VI.
The front panel of the VI (Figure 24 above) is designed to show the potential and the current in two
forms.
The applied potential is displayed as a function of time in chart 1. The current that results from this
applied voltage is displayed as a function of time in chart 2. The more traditional polarographic
display is evident when current is displayed as a function of applied potential (rather than as a
function of time) in XY chart 3.
The XY chart is equipped with cursor controls (4) that later are used to measure the half wave
potentials and the diffusion limited current for qualitative and quantitative analysis.

18
The front panel also contains the controls that are needed to cause the potential to scan as shown,
plus other functions. For example, a switch is provided (6) to determine if the potential should be
scanned (as shown) or simply held at some initial value (11). The scan polarity can be set to be
cathodic or anodic with switch #5. The range of potential scan is determined by the final voltage
setting (12). When the VI is used with solid electrodes (instead of mercury) the scan usually starts at
some anodic initial voltage. This is set by the slider (10) as an initial anodic offset voltage.
The scanning voltage waveform is made using a cyclic function generator. To get a wave such as
shown here, only one half of a complete cycle is needed, and this is entered in control #14. There
are other possible waveforms to use for the scan. All waveforms are selected from the menu in
control #13.
The output potential does not scan smoothly. The D/A output is discrete, i.e., it occurs in steps. The
size of the step, E, and the time for which it is constant, t, is determined by the settings in
controls #15 and #16. This determines how long the drop is allowed to grow before the current is
read. Shortly after the current is read, the drop is detached.
The switches needed to turn on the drop knocker (17), the vacuum pump to aspirate out the cell
contents (18) and to turn on the nitrogen gas for deaeration (19) also are on the front panel of the
VI. These switches are queried only when the VI is first started, so it usually is best to turn the scan
switch #6 off, turn on the other switches desired, and then start and stop the VI. A bit of practice in
the lab will make this more clear.
Saving data to a spreadsheet for subsequent plotting and other manipulations is important. A button
is available (#20) to allow this. When it is depressed, the data shown in the XY plot (23-24) will be
written out to a file as named in path control #21, but not until after the scan has been completed. If
the scan is interrupted before it is plotted on XY graph 3, then nothing is saved. If the file name is
not changed between runs, then the new data are appended to the old, i.e., the file is not
overwritten, but just becomes longer.
The controls for smoothing (8,9) will be mentioned later. Half wave potentials and related currents
can be read by adjusting the positions of the cursors with the fine position diamond control (22), or
by simply dragging the cursor with the mouse. Readout (4) will show the cursor intersections.
The data shown on graph (3) in Figure 24 are for a solution containing 0.001 molar Cu+2 and 0.001
molar Zn+2 in 0.1 molar KCl and 5 drops of 0.2% Triton X-100. Wave 23 is for copper, and 24 for
Zinc.

19
The VI Diagram
The diagram for the potentiostat VI as set up for polarography is shown in Figure 25 below. There
are four parts to it. At the left are shown the sub-VIs used to generate the voltage scanning
waveform. In the middle is the FOR loop containing the frames used to do the timing sequence and
data acquisition shown previously in Figure 23. The right hand side contains the file writing and
smoothing routines. To build the VI, or understand it better, it is the central FOR loop that needs to
be understood first. The other functions follow from that.

Figure 25 The LabVIEW VI potentiostat diagram as used for polarography.

The first frame in the central sequence is shown in Figure 26. It is used to turn on or off the vacuum
pump or the nitrogen gas flow valve. This are wired into digital byte zero on device 5 using bits 1
and 2 of the byte.
Whether they are turned on or off depends
on the state of the Boolean control shown.
This is set by the switches 16 and 17 on the
front panel.
Thus, if you have decided to build this VI,
you should lay out the front panel first, and
then find the appropriate controls to wire in
the diagram.

Figure 26 Gas and vacuum digital lines

20

A
Solenoid
P

I
S
AC

B
P

AC

Figure 27 Sequence frames used to operate the drop knocker

Two sequence frames are needed to operate the drop knocker, and these are shown in Figure 27
above. The drop is detached in frame 1 when digital bit 0 is made true, and held that way for 0.1
second. This causes power to be applied to the drop knocker solenoid, extending its plunger and
causing it to strike the side of the cell. In frame 2, the same bit is set false, opening the circuit to the
drop knocker solenoid. The plunger is spring loaded so that when power is removed from the coil it
retracts inside it.
Some practical work was done to determine that power needs to be applied to the solenoid for 0.1
second. Less than this leads to taps on the cell that are too light to be effective. Times longer than
this cause the solenoid coil to heat up. In some cases, the coil can burn out if power is kept on it for
too long.

21
Once the old drop has been knocked off,
and before the new drop has had an
appreciable chance to grow to a fragile
geometry, one step of the potential scan
either is, or is not, applied to the electrodes
through the NB-MIO-16L D/A converter.
Figure 28 shows the case where we wish
the potential to increase cathodically. The
output of the function generator is simply
passed through the TRUE case and
presented to the AO sub-VI. Channel 0 has
been selected on device 5. The voltage out
is read by the AI MULT PT Sub VI and
averaged before being displayed. Channel 1
is used.

Figure 28 Applying a cathodic scan

It is quite important that the voltage be

presented to the electrodes before the
mercury drop has had a chance to grow
appreciably. If it is larger, then the sudden
application of a change in voltage to its
surface can cause the surface to stream and
flow sufficiently that the drop will be
dislodged.

Figure 29 shows the case where we do not

want to scan the voltage. Each element then in the function generator
output array is multiplied by zero. There then are no changes in the
timing.

Figure 29 Not applying

a cathodic scan
Note that frame 3 is held up until the timer
interval set by the front panel controls has
elapsed. It is during this time that the drop
grows. The drop area increases, but the
potential is held constant on it by the
potentiostat output.
When frame 3 has timed out, frame 4
executes. Here, the current is read. The AI
multi-point sub-vi takes 500 readings of the
current at 5000 readings per second, and
passes the resulting array to the averaging
sub-vi. Such an approach is needed to
compensate for the rapid fluctuations in the
surface of the mercury drop, which is itself

22
flowing as the drop grows. A single reading would not be at all reproducible from drop to drop.
The result is multiplied and offset for display,
and passed out of the frame.
The manner in which the different waveforms are
generated to make the scan is interesting. This is
shown in Figure 31.
A sub-VI is used to generate the waveform. It
can output a triangle wave,
, a sine wave,
Figure 31 The waveform generator sub-VI

, a sawtooth,
, or a square wave,

. In our work, we almost always used the

triangle or sawtooth waveforms, although it

might be interesting to try a sine wave sometime.

The sub-VI outputs a complete waveform array at once. The number of points in the array, the
variation in amplitude between them, and the number of repetitive cycles of each are all set by
external controls or constants, as is the symmetry of the waveform and its phase.
Note in Figure 31 that the Initial Voltage and Final Voltage controls simply set the amplitude of
the selected waveform.
The number of output points from the function generator array is the same as the No. of Steps
input control. The first operation on this array is to rectify it with an absolute value function. This
makes all values positive, and has the effect of doubling the frequency. This is why the Cycles
control is set to half of what would intuitively seem to be the right number.
The potentiostat does not achieve any timing capability from the function generator sub-VI, since it
outputs a complete array of points, essentially instantaneously. Timing is achieved when the array is
passed to the FOR loop. The FOR loops in LabVIEW are self-indexing. If an array of 100 points is
wired into one, then it will automatically execute 100 times. If the array has 200 points, then the
loop will execute 200 times. Within the for loop, the Wait milliseconds clock delays the sequence
frame that outputs the potential (Figure 28 and 29), and this is where all of the timing originates.
For future development work, the array of waveform points is completely available. For example,
the direction of the scan in this VI is always from anodic to cathodic. This can be changed by
multiplying the array points each by -1. The starting potential also can be set either anodic or
cathodic by adding a constant to each. The scan can be made logarithmic, have other signals added
to it at higher frequencies (e.g., for AC polarography), or be pulsed for pulse polarography by
offsetting groups of points. This mode of primary signal generation is flexible and simple, a true
plus for the LabVIEW approach.

23

Figure 32 The Savitzky-Golay algorithm for smoothing data in an array.

A particularly interesting feature of this potentiostat is the ability to smooth the sampled current
points before saving or plotting them. This kind of smoothing is referred to as digital signal
processing, and provides noise cancellation over the complete scan. The multiple sampling and
averaging done when the current is first measured does not, since it applies to a single time in the
lifetime of a single drop.
Smoothing is done here using a Savitzky-Golay algorithm, implemented in LabVIEW by Dan
Gilmore of the Chemistry Department at the University of Arizona. This algorithm is based on
doing a running average over a variable number of points in an array. But, instead of just calculating
a simple average, each of the points in the set is first multiplied by a weighting factor that makes
the net average over the set approach a least
squares error minimization optimum value. The
number of points in the weighted average is set
with an external control, but the coefficients are
all pre-calculated and loaded permanently into a
concatenating routine, as shown in Figure 32 for
19 points. This smoothing routine is both fast
and effective.
The SG smooth is a sub-VI that is simple to
wire. The routine used here is shown in Figure
33. The output also is an array, which may be
taken directly to a plotting routine.
Figure 33 Wiring the SG smooth sub-VI

24
How the Potentiostat Gathers and Presents Data to its Display
To see how the VI works to give a smooth display from a dropping electrode, where the drop area
changes continuously as a function of time, some expanded scale recorder tracings were prepared to
accompany the brief explanation given previously in Figure 23. These follow here.

Figure 34 Composite illustration of DME behavior

In Figure 34 are shown the actual polarogram of an 0.001 M solution of Cd+2 (center), an
expanded view of the individual drop behavior near the start of the wave (left), and the sampled
current/potential diagram obtained using the potentiostat VI (right). Observe the center polarogram.
The current rises and falls as the potential is scanned, and as the area of the drop increases with time
until the drop knocker finally detaches the drop.
The behavior of individual drops (left inset) is interesting. The current rises as the drop area
increases. Keep in mind that the applied potential is held constant during this time. Just before the
end of the drop life the current is read. Then the solenoid of the drop knocker is actuated, and the
drop falls off. Note that there appears to be a small period of time when the current is rising,
followed by a sudden increase. This is best understood by inspection of Figure 34B on the
following page.

25

Figure 34B Expanded view of drop detachment transients

Here it is evident that after drop detachment the current begins its expected slow increase due to
increase in the drop area. But, the next potential then is applied, suddenly. This causes a surge in
the current (the so-called charging current) followed by a transient dip. The current then starts
increasing at the new potential as the drop area increases. The small noise transients near the end of
the drop life are hard to diagnose, but may be associated with physical oscillations in the drop.

26
Analytical Lab Work
You will be working as a Software/Chemist team when doing this lab. There are two DME
polarograph stands, and each team will have access to one of them.
There are several analytical projects that can be explored in this lab. They are:
1.

Determine the concentration of an unknown sample, using a set of standards to make a

working curve.

2.

Determine the effects of adding an unregulated amount of a maximum suppresser to the

presence of determinate error in determining a set of unknown samples.

3.

Determine the effects of unregulated amounts of deaeration on the expected accuracy of

analyzing a set of unknowns.

4.

Determine the effects of variable amounts of acid in an unbuffered solution on the expected
accuracy analyzing a set of unknowns.

5.

Determine the effects of other cations present in a natural sample matrix on the expected
accuracy analyzing a set of unknowns.
Project 1 - Determination of Unknown Concentration

This is the classic application for which the Nobel Prize was awarded. It is based on the fact that
under diffusion control, in an unstirred solution, the limiting current is directly proportional to
concentration of the reducible species.
To help Chemist with meeting this objective, a set of cadmium solutions and an unknown have
been prepared ahead of time for you. This means that all that Chemist has to do is load the cell
with the appropriate solution, add Triton X-100 maximum suppresser, deaerate, and let Software
take the scan and save the data. After that, Chemist would empty the cell using the aspiration pump,
refill it with another solution, and repeat the process. Software would compile a working curve
from the polarograms, and use it to determine the concentration of the unknown.
The recipe for the solutions is as follows:
Concentration
0 in KCl blank
0.0004 M Cd+2
0.0008M Cd+2
0.0012 M Cd+2
0.0016 M Cd+2

Ml. to add
~ 50
~ 50
~ 50
~ 50
~ 50

X-100 to add
6 drops
6 drops
6 drops
6 drops
6 drops

N2 time
10 minutes
10 minutes
10 minutes
10 minutes
10 minutes

Aspirate to
waste bottle
waste bottle
waste bottle
waste bottle
waste bottle

The unknown solution uses the same recipes as the standard solutions.
It will take some time to run these standards. During this time, all of the conditions in the
experiment must remain constant. One of the things that you should attempt to determine is over
what length of time the experimental parameters do in fact remain constant. I did some work this
summer and found that the data shown in Figures 35 and 36 occurred. This convinced me that you
should be able to hold your experimental conditions constant enough to do this determination for at
least a period of 2 to 3 hours.

27

Figure 35 Polarograms of Cd+2 at various concentrations for making a working curve.

Oxygen Reduction

Net Limiting Current

Residual
Current

Figure 36 How to use cursors to determine net limiting current.

With data such as the

above at hand, the trend
line function can be used
to draw straight lines
through the limiting
current and residual
current regions, and from
them the net diffusion
current calculated.
Alternately, you may
want to use the cursors
that are available on the
front panel of the
potentiostat VI, and set
them to read out the net
diffusion current.
An example is in Figure
36. One cursor is put in
the residual current
region. The other is put in
the limiting current
region, but not where
oxygen would be
reduced. Their difference
is the net limiting current.

28

Figure 37 Cd working curve, taken from polarograms run over several hours
When the data are taken properly, using either a spreadsheet or the cursor method, the results can be
impressive. For example, in Figure 37 is shown one working curve that was prepared from
polarograms taken both in the morning and the afternoon. A straight line with good regression data
resulted, even though the DME was stopped and the system shut down for lunch, and restarted
from scratch after that. The DME characteristics, and all of the electronic settings, obviously held
over this long a period. Such performance cannot be guaranteed, but with careful techniques it
should be possible to determine several unknown concentrations over a full days work when the
standardization is done at the start of the day.

29
Project 2 - Effects of a Surfactant on Analytical Results
In preparing the solutions to use in meeting the first objective, you added 6 drops of a surfactant
called Triton X-100 to each solution. In the past, other compounds like gelatin also were added.
The function of these compounds is to coat the surface of the mercury drop as it forms with a
substance that will stabilize the flow that it undergoes while expanding. Mercury flows into the drop
from the inside, and then circulates inside of it. It swirls outward as the drop grows, and causes the
surface itself to flow. This leads to mixing in the immediate vicinity of the drop surface, and eddies
and cavities form in the solution that produces irregular streaming along the drop. All of this can
produce strange, non-diffusion effects when the potential is sufficiently cathodic that the surface
concentration of the analyte is approaching zero.
When a surfactant is added to the solution, the streaming effects at the drop surface are minimized,
and the polarographic wave approaches the limiting current smoothly. We expect then that there will
be better analytical results.
Consider the data shown in Figure 38 below.

Figure 38 Effects of 6 drops of Triton X-100 on 0.0016M Cd+2 polarogram

The effect of adding X-100 is clear in Figure 38. To explore is how much of a difference this makes
when an uncontrolled amount of X-100 is added to an unknown whose concentration is to be
determined from a working curve made with standards that have reproducible amounts of X-100
added. In other words, how critical is the concentration of X-100 in solution on the accuracy of the
method?

30
Project 3 - Effects of Deaeration Time
Dissolved oxygen in test solutions has always been a headache in polarography, and in its
variations. Oxygen is reducible in two steps according to the follow half-reactions:
O2 + 2H 2 O + 2e- H2 O2 + 2OH-

E1/2 = -0.1

H2 O2 + 2e- 2OH-

E1/2 = -1.1

These two waves are irreversible, and drawn out over virtually the entire cathodic range. They also
are pH dependent, and will change height with mechanical agitation of the solution as oxygen is
mechanically displaced.
Our book, unfortunately, is not clear on what the oxygen waves will look like at a DME in just a
solution of supporting electrode. Figure 39, below, was scanned from Bard and Faulkner to give
you an idea of what to expect in our lab.

Figure 39 Oxygen waves at a DME scanned from Bard and Faulkner

The question posed in this objective is not if oxygen produces waves that clutter the cathodic region
of the polarogram that we use to analyze for Cd+2 . Rather, it is how big a problem this will be? Will
the presence or absence of oxygen in solution make a difference in the accuracy with which we can
measure the concentration of Cd+2 in a series of unknown samples?
Oxygen can be sparged from solution by bubbling a stream of nitrogen through it. There is always
a question of what flow rate of nitrogen to use, whether to saturate the nitrogen stream with water

31
before passing it into the solution, how much to disperse it, how long to pass it through the
solution, and whether to blanket the solution with it after the deaeration has been done. Another
important question is whether to deaerate the solutions to be analyzed in a separate part of the
analysis (say, in a set of bottles before adding them to the cell), or to wait until the actual analytical
aliquot is in the polarographic cell and deaerate it there.
An example of one way to explore this objective is shown in Figure 40. Here, a Cd+2 test solution
was scanned both with and without deaeration. While there was little control over the design of the
study, it did show where the greatest obvious effect of deaeration would be on the Cd wave.
Clearly, you can come up with much better approaches.

Figure 40 A simplistic look at the effects of deaeration on the Cd+2 wave

When working on this objective, the question of timing the deaeration is at issue. Should the time be
regulated, and, if so, how well? Is it enough to simply deaerate for more than some critical time? If
complete deaeration is desired, will the time to achieve it make the total analytical time for a set of
samples too long to be used in a quality control situation?
In exploring this effect, pose your questions well. I am especially interested in deciding if robotic
sample preparation could be done, and, if so, could deaeration be done outside the polarographic
cell as part of the sample preparation. I also wonder of there is a way to measure the Cd+2 diffusion
current so that deaeration is not needed at all.
When you use the apparatus that we have assembled here, try to avoid letting the way that we have
built deaeration into it influence your thinking too much. There certainly are other possibilities.

32
Project 4 - Effects of Solution Acidity
Consider the half reaction :
2H+ +2e- H2

E1/2 = - 1.5

This implies that small and variable amounts of hydrogen ion could have an effect on the Cd+2
analysis. The fact that the half-wave potential is significantly larger than that for Cd+2 /Cd does
however suggest that it might not be a problem. Most chemists know though that running
unbuffered solutions raises problems in general with CO2 absorption. So, we need some ideas of
what the effects of [H+] will be on the analysis.
To gain some experimental ideas, I suggest that you study the poster outside SC328. Some strip
chart recordings that indicate at least one effect of [H+] are shown there. Also, since the supporting
electrolyte for the Cd+2 standards is KCl, the addition of small (0.001 M) amounts of HCl seems
sensible.
Again, the idea here is not just to observe the reduction of H+. Instead, we need to know if control
of the amounts of [H+] in a series of natural samples is important. And, always remember, there
may be ways to measure the diffusion current that eliminate the need for such control.
Objective 5 - Effects of a Natural Sample Matrix
In Figure 41 above is shown the polarogram of a mixture of cations. This, in one step, shows what

Figure 41 Polarogram of a mixture of reducible cations

the problems could be in using polarography to analyze natural samples. Suppose, for example, that
the sample we were interested in monitoring was an effluent stream from some industrial process
suspected to be putting Cd+2 into the environment.

33
If the sample were collected downstream from the source, the chances are excellent that it would
have dissolved some of the soil over which it was flowing. This would contribute transition metals
to the sample, among other things. We thus could expect variable, and largely unpredictable,
contamination of the natural sample with Cu+2 , Ni +2 and Zn+2 cations, since these are common to
soils. Since we would hope that there would not be significant Cd+2 in the sample, it might even
occur that the contaminants would be present at a higher concentration than the analyte. Such is the
nature of a matrix effect.
The central question is what effect variable amounts of these contaminants would have on the
analysis. Note in Figure 41 that the 0.1 M NH4Cl supporting electrolyte has buffered the solution to
be basic. This extends the range of the DME cathodic scan enough that all of the cations produce a
detectable wave.
As you explore this objective, keep in mind that you can measure the diffusion current from these
ions separately. You also can transfer the data to a spreadsheet, and in a series of columns literally
subtract out the current from one cation from the net current produced by more than one. These kind
of manipulations presuppose a linearity between diffusion current and concentration for all of the
cations, but, given the excellent behavior for Cd+2 , this does not seem and unrealistic assumption.
Again, keep in mind the central objective. How does the presence of unpredictable amounts of
contaminant cations, such as those shown in Figure 41, effect the accuracy with which Cd+2 can be
determined?
Project 5 - A Class Project
The entire class can do an interesting project that relates to mixtures. Each lab section will have to
make up a set of solutions that constitutes one part of a larger mixture. The section will then take the
polarograms of each set of solutions, and pass the data on, via the Analytical Chemistry server, to
the next section. At the staff meeting in the following week, the data can be assembled to complete
the project.
As an example of this kind of project, view the figures on the following pages. Solutions were
prepared that had a base concentration of copper, and to each were added increasing amounts of
zinc. The question that was to be answered was, Could varying amounts of copper be determined
in solutions that had varying amounts of zinc in them, and could varying amounts of zinc be
analyzed in solutions that had varying amounts of copper in them?. While the solutions were not
hard to make, they took at least 20 minutes each to deaerate, and about 10 minutes to scan, so each
set of data took an afternoon to gather.
A class project that could be done involving the same kind of question would be to use cations other
than copper and zinc. You would refer to a table of half wave potentials (in the Science Library) to
select these ions.

34

Quantitation of Cu +2 Limiting Current

0.225
Residual
10 ppM Cu
20 ppM Cu
30 ppM Cu

Current follower output voltage (1 Amp/division)

0.200
0.175
0.150
0.125
0.100
0.075
0.050
0.025
0.000
-0.025
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

Ecathodic vs. SCE

Figure 42 These data would be used to determine if Cu can be quantitated alone.

Variable Zinc, Fixed Copper, pH = 3.7

6/17/97 - John Walters - Bronze Analysis Development Study
0.250

Current Follower Output Voltage (0.5 Amp /division)

0.225

0 ppM Cu 0 ppM Zn
10 ppM Cu 0 ppM Zn

0.200

10 ppM Cu 10 ppM Zn
10 ppM Cu 20 ppM Zn
10 ppM Cu 30 ppM Zn

0.175
0.150
0.125
0.100
0.075
0.050
0.025
0.000
-0.025
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

Figure 43 These data would be used to determine if Zn can be quantitated in the presence
of 10 ppM Cu.

35
Variable Zinc, Fixed Copper, pH = 3.7
6/18/97 - John Walters - Bronze Analysis Development Study
0.325
0 ppM Cu 0 ppM Zn

0.300

Current Follower Output Voltage (0.5 Amp /division)

20 ppM Cu 0 ppM Zn

0.275

20 ppM Cu 10 ppM Zn

0.250

20 ppM Cu 20 ppM Zn
20 ppM Cu 30 ppM Zn

0.225
0.200
0.175
0.150
0.125
0.100
0.075
0.050
0.025
0.000
-0.025
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

E cathodic vs. SCE

Figure 44 These data would be used to determine if Zn can be quantitated with the same working
curve slope and intercept in the presence of 20 ppM Cu as was observed with 10 ppM Cu.
Variable Zinc, Fixed Copper, pH = 3.7
6/17/97 - John Walters - Bronze Analysis Development Study
0.450
0.425
0 ppM Cu, 0 ppM Zn

0.400

30 ppM Cu, 0 ppM Zn

Current Follower Output Voltage (0.5 mAmp /division)

0.375

30 ppM Cu, 10 ppM Zn

0.350

30 ppM Cu, 20 ppM Zn

0.325

30 ppM Cu, 30 ppM Zn

0.300
0.275
0.250
0.225
0.200
0.175
0.150
0.125
0.100
0.075
0.050
0.025
0.000
-0.025
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

E cathodic vs. S.C.E.

Figure 45 These data would repeat the Zn quantitation question with 30 ppM Cu.

1.4

36
Reporting the Results
Different teams in the class will select these objectives. Many of them will be done on different lab
days. To report out the results of all of them, a special Monday meeting will be scheduled to allow
short 10-minute presentations, with appropriate visual aids, of what the conclusions are.
Asking that an elected class representative present an answer to the question, Is polarography an
effective analytical method for the routine determination of sub-millimolar amounts of Cd+2 in
natural samples, will emphasize whole class communication?
This is one of several lab section laterals that we will do this semester. Success in an experiment
like this requires that the people in one lab section communicate ahead of time to those in the next
what has happened to them and how well the results met their expectations. Good communication
can be done by e-mail while the lab is being done. The analytical Chemistry server can be used to
drop ship results, or they may be attached to an Eudora message.
The reason for such efforts is shown on the next page in the form of a survey done by Dr. Robert
Gentry of the University of Minnesota. No matter what you have done, how you share it with
others is the most valuable skill you can have.

37
Dr. Ron Gentry, Chair of the Chemistry Department, reported the following material to Chemistry
faculty and students of the University of Minnesota on October 4, 1994. In an accompanying
memo, he stated:
A committee of the Council for Chemical Research this year polled major chemical
companies about the characteristics they look for when assessing M.S. or Ph.D. job
candidates in chemistry and chemical engineering. Attached are the responses, which should
be interesting and helpful for those preparing for industrial interviews.
When seeking a graduate degree level (M.S. or Ph.D.) candidate in Chemistry or Chemical
Engineering, which of the following are most important characteristics?

Thesis Topic
Thesis Advisor/Professor
Academic Institution Granting Advanced Degree
Grade Point Average - Graduate School
Grade Point Average - Undergraduate School
Undergraduate School
Undergraduate Discipline/Curriculum
Communications Skills
Extracurricular Activities
Foreign Language Skills
Professional/Honor Society Membership
Papers Presented (Number)
Publications (Number)
Computer Skills
Participation in co-op Programs
Full/Part-Time Employment in Major Field
II.

Most Important -> Least Important

5
4
3
2
1
10
28
20
10
1
13
26
20
8
2
16
39
12
1
1
13
31
18
5
2
12
31
20
6
0
2
16
30
19
1
6
27
24
9
2
39
31
0
0
0
0
7
33
23
6
2
6
25
23
12
0
3
24
25
16
1
13
30
15
9
1
18
26
14
10
2
30
29
8
0
3
23
22
16
5
11
24
23
10
1

Which of the following traits are Important?

Independence
Self Motivation
Good Problem Solving Skills
Team Player
Enthusiasm
Decision Making
Professionalism

21
57
55
43
36
27
26

31
11
11
18
24
29
20

13
0
2
5
6
10
17

1
0
0
2
1
1
3

0
0
0
0
0
0
2