edited by
Inventory Control
Construction of a Photoelectric Colorimeter and
Application to Students' Experiments.
Tsulomu Matsuo
KobeTechmcal College
Ma~kDdaiTarurn#-kuKobe 655. Japan
Aklhlko Muromatsu, Kazuko Katayama, and Minako Morl
Facuky of Education
Kobe Un~vers~ty
NadaXu Tsurukabuto Kobe, 657. Japan
In recent years the functions of chemical measuring in-
struments have advanced remarkahly. Though they have
heen miniaturized, they are high-performance instruments
owing to the introduction of the electronic circuit andmicro-
computer technology. The chemical measuring instruments
for students have also progressed. Now students use the
same instruments in use a t commercial companies or lahora-
tories. Since the commercial measuring instruments are de-
veloped for rapidmeasurement and easy operation, the mea-
surement is performed hy only pressing some keys on the
instruments. However, these instruments are unsuitable for
beginning students who are learning the principles of mea-
surement. The history of research and development of
chepical instrumentation took some time before high-level
instruments were produced. They have been improved step
by step from the early stages to the modem advanced type
we now use. Therefore, we must give students the instru-
ments that will help them understand the principles of mea-
surement, and also, we must leave room for improvement
and innovation on the student's part. Therefore, the instru-
ments for students must be different from the commercial
type.
Many teachers are acquainted with the SPEC 20. We have
developed the photoelectric colorirneter (PEC) ( I ) , which
can he assemhled by the students themselves. The PEC can
do much the same work as the SPEC 20, but a t a greatly
reduced cost. The level of its measuring technology is from
an earlier period; however, i t is sufficient for the student's
experiments. Formerly, the handmade instrument could not
compare with the commercial ones in function and accuracy.
But, with the new electronic circuit elements and electronic
parts, the function and accuracy of handmade instruments
are comparable to commercial ones. Since the development
of the spectrophotometer, the PEC is not frequently used.
But the fundamentals of the spectrophotometer were based
on the PEC. Therefore, beginners must get used to the PEC
first, so that they will understand the principle of absorptio-
metric method. For example, one of the attractive points of
chemistry for the students is the varied and beautiful colors
of the solutions. The students are impressed by the color-
ation after the mixing of colorless solutions. The PEC is an
instrument that examines quantitatively the color change in
the solutions. I t can be used for quantitative analysis and
also used for the verification of various chemical principles
in student's experiments.
Principle of Colorimetry with PEC
According t o LamhertiBeer's law (2),the absorhance is
expressed as
A = log UdI)= cbe (1)
where A is the absorhance, loand I are the intensity of the
JOE RICH
Blackhawk Christian School
Fort Wayne. IN
incident light and transmitted light, respectively, f is the
molar absorptivity, b is the cell path length, and c is the
concentration of the solution. Though the assembled PEC
can measure the transmitted linht intensitv, it cannot mea-
sure the incident light intensit;owing to the optical system
of the assembled PIX. Thus Lamhert-Beer's law cannot he
applied an it is. Then, by independently applying Lamben-
Beer'slaw to the solution and thesolvent systems, theabsor-
bance with the use of PEC can be derived as fnlluws:
A = log (I'lI) = ebe (2)
where I' denotes the transmitted light intensity for the sol-
vent and I denotes that for the solution. Accordingly, by
measuring the values of I and P, the absorbance of the
solution can be derived: that is, with the measurement of the
light intensity for the solventand test solution, the absor-
bance can be determined.
In the case of the assembled PEC, I and I' are measuredas
the output voltages, which are proportional to each light
intensity. Then the absorbance is given hy
A = log (E'lm = rbe (3)
where E' is the output voltage for the solvent and E is for the
test solution.
This explanation of the principle of measurement with the
assemhled PEC must be given to the students before they
use it.
Construction of PEC
The PEC was designed to help in the understandingof the prinei-
ple of spectrophotometricmethod and to he assembled by the stu-
dent with ease. Special attention was paid so that it would be able to
he assembled without special ability by student.
Modern commercial electronic parts were sufficiently used and
were put to new use in the PEC. By using the light-intensity sensor
and OP amplifier (3), the teacher or student can assemble it and
ohtain the same expected quality.
. . The cost was also taken into
account.
The side view of assemhled PEC is shown inFieure 1.EachDart of
PEC is described below. Part A in Figure 1 is thipowrr supdly and
amplifier for the lighr-intensity sensor; it sits in a aluminum box
('251) X 150 X 60 mm). H is theoptical system consistingof n lnrnp,a
cell, and a light-intensity sensor, and these can be seen hy removing
the side cover. The principle of the absorptiometrie method is easily
\
10 8
Figure 1. Side view of assembled photaelechic colorlmeter (PEC); A,, Power
supply and amplitlw: 6, optical system.
Volume 66 Number 4 April 1989 329
understood by observing the light passing through the test solution.
.~~
1is a lamo with the~~~.
~~ ~ small lens 12.2 V.. 240 mAl~for the lieht
. source. 2
is the diaphragm of the plastic plate (center radii, 1.O-3.0 mm). The
radius was chosen to give the highest absorbance according u, the
concentration of thesolution. Thesmall radiusgiver high sensitivity
for quantitative analysis hut the stability of output voltage hecomes
critical. 3 is a filter of colored cellophane, which can he exchanged
according to the color of the test solution. 4 is a plastic cell (1 = 10, w
= 10, h = 45 mm). This cell is same size as far the spectrophotometer
but venr chean. 5 is a diaohraem. .. (3. mm) for the lieht-intensitv
sensor. It shades the stray light. fi h a light.inten*ity sensor ( I S ,
SiemensTFA 1001W).7 is a cell stand of the silicon rubber stopper,
thesameshape as the bottom of theceil that fits into it.The plny of
the cell must he minimized for the accurate measurement of the
absorbance. 8 is a coarse control knob for the sensing of light intensi.
ty. 9 is a fine control. 10 is the power switch.
On assembling the PEC, electronic parts themselves were effec-
tively used, and only the metallic parts supportingthe lamp and LIS
needed some treatments. The lamn must be keot aoart from the cell
(3-4cm) in order toohmin the light beam.7'h;l.l~ is better located
close to the cell. The lamp, the cell, and 1.1s must be aligned to
acquire maximum light intensity. The critical adjustment of their
mutual position was performed by measuring the light intensity.
The adjusted beam Light produces high sensitivity in the measure-
ment of ahsorhance.
The electronic circuit diagram of the amplifier for measuring the
light intensity is shown in Figure 2. The LIS is an IC consisting of a
photodiode and amplifier. When it receives the light, a current
proportional to the Light intensity is ohtained (1Lx = 5 FA, 0-40000
L 3 . If R, is selected accurately to be 200 0, a 1 mV potential
corresponds to 1 Lx. As the output potential of LIS is low (0300
mV) at usual measurements of ahsorhance, it must be applied to the
amplifier so as to measure with the usual voltage meter (&3 V). The
first step of the amplifier turns aver the polarity of output of LIS
and operates as a buffer amplifier. The second step amplifiesit up to
15 times. At usual measurements the output voltage for pure water
is adjusted to 3.00 V with the come and fine control knobs. For the
power supply of the amplifier, a switching regulated power supply
(ELCO, KMC-13, f12 V, +5 V) was used. Any power supply is
applicable if the capacity (f12 V, 0.1 A; +5 V, 0.5 A) is fulfilled.The
power supply for the lamp must be regulated to avoid the drift of the
light intensity. A voltage variable regulator circuit (0-5 V) shown in
Figure 3 was used, and thevoltage is accurately adjusted to 2.20 V by
VR,.
Fiwe 2. Electronic circun diagram of ampilfler for measuring light intenshy;
LIS, llgMlntenshysensor,TFAlOOlW, OP = pA741, VR, = coarsesense; VR2
= finesense: VR. = gain.
Flgve 3. Elemnic circuit diagram ofwltage vsrlable regulator fa lamp; VR,
= voltage adjuster.
330 Journal of Chemical Education
Experiments as Teaching Activities in Using PEC
Electric Characteristics of PEC
As described above, the output voltage of PEC must he
proportional to the transmitted light intensity. T h e correla-
tion between the output voltage and light intensity was ex-
amined hefore the exoeriments took olace. T h e lieht intensi-
ty was changed hy placing some colored cellophane in the
PEC celland theoutout voltare wasmeasured with adieital
multimeter (SOAR ME-530). I\ standard voltage meter73 V
full scale) was also used simultaneouslv to measure the ten-
dency of the ahsorhance change. he light intensity was
determined from the R1 potential (1mV = 1 Lx), and the
output voltage was the voltage after amplification. The re-
sult is shown in Figure 4, and i t is found that the output
voltaee is ~rooortionalto the lieht intensitv. Therefore.
~d~.the ~~~
~ ~
abso;bance c k he determined from the measurement of the
output voltages for the solution and the solvent with PEC.
Calibration Graph
T h e calibration eraoh for Cu2+ was obtained to confirm
the possibility of q;aniitative analysis hy using PEC. All the
chemicals used for the exoeriments were of analvtical made.
I n order t o get a high sensitivity for C U ~ +&,I ex&s of
ammonia was added t o Cu2+ solution t o form ammine com-
plexes. AO.l mol/LCuS04 stock solution, which isntandard-
ized by 0.1 mol/l. EIYI'A soluti(m was used. T h e ahsorhance
was calculated from the output voltages for pure water and
test solution by eq 3,Thestraight calihrationgraphshown in
the Figure 5 was obtained with a red filter, and this indicates
that the PEC can be applied to the quantitative analysis of
the colored solution. As the deviation from the straight line
heginsat about 5 X lo-' mol/L, this concentration is consid-
ered to he the lower limit of the auantitative analysis of
Cu2+. Thus the sensitivity of PEC & considered to be rela-
tively high.
Similarly, the straight calibration graphs for NiZf and
Fe(I1)-o-~henanthrolinewere ohtained. Therefore, i t has
been proven that PEC can he used for various experiments
including the coloring of the solution.
0 50 100 150 200 250
Light Intensity / Lx
Figure 4. Conelation between ilght i.ntenslty and output voltage.
 I I I I I I I I I I
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
[Cult / ([Cult CEOTAIt)
~ l g v 5. (ammonia mettmd); filter = red.
e Callbratlm graph for C U ~ + Figure 6. Comlnwxrs variation memod for Cu(1lkEDTA system: finer = red.

Composition of Complexes sured. A platinum plate (1.0 X 4.5 cm) and a carbon rod (core
If the compositions of the complexes are experimentally of pencil 3.5 an in length) are used for the cathode and
determined, the students can try to estimate the coordina- anode, respectively. A variable, regulated power supply was
tion number of the metal ions and ligands and the structure used, and the voltage was manually adjusted to obtain a
of the complexes. Then the composition of Cu(I1)-EDTA constant current (9.5 mA).
was determined hy continuous method (3) at a total molar A 0.1 m o l b CuSOl solution was electrolyzed, and its ah-
concentration of0.01 mol/L. The result is shown in Figure 6, sorhance was measured. With the electrolysis proceeding,
and it is found that the composition ratio of Cu(II)-EDTA is the absorbance of the solution is gradually decreased, as the
1:l judging from the molar ratio of the absorbance peak line in Figure 8 shows. The concentration of Cu2+ under
([Cu]J[[Cujt + [EDTAItJ= 0.5, t = total concentration). This electrolysis was determined hy the calibration graph for
compositionratio is the basis of the calculation for the chela- Cu2+.From the variation of the concentration of Cu2+by
tometric titration by using the standard EDTA solution. electrolysis, the Faraday constant is determined as 94330 C.
The composition of Cu(I1)-NTA (NTA = nitrilotriacetic This value deviates from 96500 C by only 2.3%.
acid) complex was also examined by the molar ratio method When both of the electrodes are substituted by copper
(3). Figure 7 represents the absorhance of CuW-NTAvary- plates, the concentration of the solution is not changed by
ing with NTA concentration ([Cu2+]t= mol/L). The electrolysis. This fact indicates that anodic stripping has
absorbance is gradually increased with increasing [NTA],
but it reached a plateau at the ratio of [Cu]J[NTA]t = 1.
This indicates the composition of Cu(I1)-NTA is in the ratio
of 1:l. In addition, the compositions of Cu(NH3)aZ+,
Ni(NHs)s2+, Co(I1)-EDTA, and Fe(I1)-phenanthroline
complexes were determined, and the coordination numbers
of CU~+, NiZ+, and Fez+were estimated. Since the coordina-
tion numbers of those metal ions were estimated by using
the PEC, the student's interest in the "second atomic valen-
ce" would he increased.
Determinationof Faraday Constant
When the solution containing the electrolytes is electro-
lyzed, the concentration of the solution will he changed. The
change of the concentration owing to electrolysis is mea-
sured with the PEC and the Faraday constant is determined.
The electrolytic current is limited by the area of the elec-
trode surface. It is necessary to minimize the volume of the
electrolytic solution in order to obtain the sufficient concen-
tration change at limited Coulomb number. Therefore, the
I I I I I I I I I

cell for PEC is employed for the electrolytic cell. The volume 0 2 4 6 8
10 12 1.4 16
of the PEC cell is very small (4.5 em3),and the absorbance of [ N T A I / X 10" r n o l / l
the solution under electrolysis can be simultaneously mea- flner = red.
Flgue 7.Molar ratlo mmhod for Cu(ll~NTA~,system:

Volume 66 Number 4 April 1989 331

occurred and the total concentration of Cu2+in the solution
~~~~
is kept constant. By the experiment of&ctrolysis with the
PEC.atudentsareable u, learn that the concentration of the
solution is changed while electrolysis is proceeding.
Reaction Rate Constant and Activation Energy for Color
Fading Reaction of Phenolphthalein
Reaction rate and activation energy are taught at the
senior high school level, but there are only a few experiments
(4) to determine the activation energy. Then, as a teaching
activity, the reaction rate constant and the activation energy
for the color fading reaction of phenolphthalein are deter-
mined by using the PEC. The phenolphthalein changes to
violetred in basic solution, and then it gradually becomes
discolored in strong basic solution with the passage of time.
This color fading reaction is expressed as follows:
R2- + OH- - R3-
~~~~~~~ ~~ constant. The reaction rate constant can be also determined
from the half-life time ( 7 ) by the following relationship:
Then the reaction rate constants at 1, 12, and 22 O C were
elucidated by measuring the half-life time by fading color.
From the slope of the log k vs. 1IT plot (Arrhenius plot (6))
(Fig. l l ) , the activation energy can he evaluated asE. = 12.4
kcal/mol. Thus the PEC can be used for the experiment
determining the reaction rate constant and the activation
energy.
Conclusion
Since there are manv excellent commercial chemical mea-
suring instruments, we do not need to pay close attention to
assemblina them. But we can now assemble a comvarable
(4)
one and obtain high quality by using the new el&tronic

where R2- denotes phenolphthalein at a basic state, and R3-

denotes it at a strong basic state. If [OH-] is sufficiently
large, this reaction can be regarded as following pseudo-
first-order kinetics. As the absorbance is proportional to the
concentration by Lambert-Beer's law, the following rela- 15 -
tionship is derived for the first-order kinetics (5,6).
"
0
X

where A is the absorbance at the time t, k is the reaction rate \

constant of reaction 4, and A. is the initial absorbance for
U
R2-. One drop of the phenolphthalein solution (1%) was "C
added to 6 mL of 1.0 molL NaOH solution, and then the 0
absorbance was measured at 10-s intervals. The result is n
L.
shown in Figure 9. The absorbance is gradually decreased
with the elapsed time, and the absorbance reaches zero after
",
0
n
4 5 -
150 s. The correlation between the time ( t )and the logarith-
mic value of the absorhance (log A) is shown in Figure 10.
The reaction rate constant can he elucidated from the slope
of the line (k = 0.020 s-1).
Then the activation energy was determined from the vari-
ation of the reaction rate constant with the temperature.
The correlation between the reaction rate constant and the. 0 50 100 150
activation energy is expressed as follows (5): Time / s
Flgure 9. Abscibance varying wim fading color. One drop of phenolphthdein
solution (1%) Is added10 1.0 mol/L NaOH solution; filter =yellow.

where k is the rate constant, R is the gas constant (8.31

-
Jouleldeg mol), T is the absolute temperature, and Cis the

0
,, 5 10
Coulomb
15 20 25
30
0 50
Time / s
100

Flgue 8. CarelatIan between a b s o m c e and Coulomb number. Elemolysis F i g m 10. Conelation between time and logarithmic value of absorbance
d 0.1 mol/LCuSO,solutlon; filter =red. Same system as shown in Figure 9; finer = yellow.

332 Journal of Chemical Education

narts. On assembline the measurine instrument, imaeina-
tion is encouraged i d thinking becomes flexible, and-also
the enjoyment of learning chemistry is increased. I t has been
found that the assembled PEC has higher quality in colorim-
e t w than was expected, and manv experiments for teaching
concepts have bken peiformed. AS the straight calibration
eraphs were obtained for some metalions, the determination
of many other colored solutions is possible with the assem-
bled PEC. All the experiments described here can be used by
senior high school students or undergraduates a t the univer-
sity. The students can assemble the PEC by themselves.
From the exneriments with the assembled PEC. the stu-
dents unders'tand experimen~allythe principle of the ab-
sorptiometric method, and also rreativity will be enhanced.
Acknowledgment
The authors are grateful to Satomi Murakami and Keiitsu
Saito, Faculty of Education Kobe University, for helpful
advice with this work.
Literature Cited
1. Matsu0.T. Kagoku Kyouikn 1984.32.430.
2. Harris, W. E.; Kratochvil. B. An Infmduetionto Chemical Analysis; Saundera: Phila-
delphia, 1982;p 378.
3. Ewing, G.W. Insfrumanfd Wfhods of Chornieol Anolyaia: MeGraw-Hill; New York,

Figure 11. Arrheniu~plot for color fading reaction. Same system as shown in
Figure 9.

Volume 66 Number 4 A ~ r i 1989

l 333