David B.

Greenberg1
Engineering Department Reaction Kinetics from Conductivity Data
United Stotes Naval Academy
Annapolis, Maryland An apparatus for the student laboratory

In this paper a conductivity experi- For a circuit of this nature it can be shown that the
ment in chemical reaction kinetics is described using dc meter voltage,
an indicating type electrical instrument of simple cir- R,
cuit design. A set of calibration curves provides read- = (RXX)E1 (1)
ings in terms of either solution resistance or concentra-
tion. The instrument is of sufficient versatility to If S, the instrument sensitivity, is defined as the change
be adaptable for both introduct,ory and physical chem-
istry courses.
Conductrimetric methods for chemical kinetic studies
have been well documented in the past (2,5 , 6, 9).
In general, however, instrumentation requirements for
such work are too complicated and expensive for con-
sideration in an undergraduate chemist,ry program.
Therefore an instrument was sought which would be
relatively easy to assemble and operate, and readily
calibrated to facilitate data reduction, so that a single
laborat,ory period could serve for the whole experiment.
To meet these requirements an adaptation of a volt-
age multiplying rectifier rircuit has been devised and
successfully tested. Figure 1. A circuit diagrom of the conductivity measuring in~rument.
Part. Lirh
The Inslrument 1 6 K ohm, 1 w a n resistor, (RiL
1 90K ohm, 1 wall resistor, R,1.
The instrument is composed of two basic component 2 0.1 microfarad paper wound copocitars (C,,C J .
2 crystal diodes, such ar Raytheon type i N 3 8 .
circnits, an ac conductivity cell circuit in parallel with 1 variable outo-transformer, 1 amp., 0 - 1 4 0 volt output, such or
a dc meter circuit. I n the cell circuit the cell (solution) Pawerstat type 2 PQ 10.
resistance R. and a fixed control resistance R1 are in 1 dc microommeter, 2 0 0 microomp. movement, 3-31f2-in. dial, such
or Simpron model 25-27.
series with the 60 cycle ac power supply as shown in 1 ac voltmeter, 0 - 1 5 0 v range, such or Simpron model 55-57. Hookup
Figure 1. In the meter circuit, the multiplied ac cell wire, mounting lugs, connectors, power card, and an 84". X 1 O-in.
voltage is rectified and displayed on the linear scale of Moronite board.

a dc microammeter. Therefore, the output voltage
Em, proportional to the voltage drop across the cell,
provides a means of tracking the conductance changes
within a reacting solution. Negligible current will be
drawn by the meter provided that R,, the meter
resistance, is large compared to both R,and R..
The circuit, a half wave vokage doubler (a), operates
in the following manner. During the first negative
half cycle of t,he voltage input, capacitor C1 is charged
through rectifier 1 to the voltage El with the polarity
as indicated. In the next positive half cycle this
capacitor voltage and the source voltage add to charge
capacitor C2 through rectifier 2. Capacitor C1 is
discharged by a like amount a t the same time, its charge
being restored during the following negative half cycle.
As the process is continued, the charge added to C2from
C1 is diminished until finally the charge on C2 ap-
proaches twice the peak value of El.
' Present address: Dept. of Chemical Engineering, Louisiana
State University, Baton Rouge, La.
140 / Journol o f Chemicol Educafion
in meter reading with respect to the fractional change
in cell resistance, then
dE,
R.
Therefore an expression for sensitivity in terms of
resistance becomes:
An inspection of Figure 2 indicates that the instru-
ment sensitivity is a maximum when the value of R,
equals R,,and falls off relatively rapidly for either
very small or very large values of R.. Although this
imposes a serious limitation on the range of conductivity
measurements for a particular value of resistance RE,
the instrument is of sufficient accuracy to yield quanti-
tative results for conductivity experiments where the
value of R, varies within the range of about 3 times
the value of R1.
 Since the choice of an optimum value of R1 depends
on the actual solution resistance, some experimentation
is necessary in order to determine approximate initial
and terminal values of R, for a particular conductivity
study. R1may then be taken as a mean between these
limits. The input voltage El should be chosen to
yield a nearly full scale meter deflection a t this approxi-
mate maximum value of R,. Values of El above
about 60 volts ac are to be avoided however, for the
power dissipation requirements of the solution and the
associated heating effects become excessive. A 3-in.
diameter dc meter with a 200 microampere movement
and a sensitivity of about 1000 ohms per volt will be
more than adequate as a read-out meter. Generally,
such meters have 50 to 75 dial divisions and offer an
accuracy of better than 5% of the full scale reading.
The value of R,, the meter resistance, is not critical
but should be about 10 to 15 times the maximum value
of R..
0 i i I 1 1 1111 I I
O.IR, LOR,
, OHUS
CELL RESISTANCE. R,
Figure 2. A plat of t h e relative instrument sensitivity versus cell resistance
in terms of the control resistance R,.
For the rate of reaction experiment t o be described
below the working values of R. have been established
as 11K ohms and 0.5K ohms respectively. Therefore a
one-watt 6Kohm resistor will suffice for R1, and 90K
ohms for R,. Since the current and power require-
ments of the circuit are low, selenium rectifiers, crystal
diodes, or vacuum tube diodes may be used with equal
facility. Capacitance values for C1 and C2 are about
0.1 microfarads. Larger values tend to increase the
time constant of the circuit which results in an over-
damping of the meter, while values much lower will
cause excessive pointer vibration from the rectified
ripple voltage. Ei, the voltage input t o the instru-
ment, should be controlled by a variable auto-trans-
former or divider circuit (see any standard electronics
text) if the 60 cycle, 110 volt ac supply t o the lab-
oratory cannot he monitored. I n this case a trans-
former has been used. These components are most
conveniently mounted on an 8-in. X 10-in. piece of
masonite or plywood as illustrated in Figure 3.
The Electrode Assembly
The electrodes consist of pieces of sheet platinum
0.010 in. thick and approximately 0.40 cm' in area.
Each plate is silver-soldered to one end of a 6-in. length
of No. 14 copper wire. The wires, mounted through
holes drilled into a No. 10'/r rubber stopper, are
positioned so that each electrode plate edge is about
in. from the bottom when the stopper is firmly
placed in a 100-ml Pyrex beaker. A short length of
glass rod, cemeuted to the wires just above the elec-
trodes, acts as a brace to prevent accidental changing
of the electrode geometry. A thermometer (-15°C
to +50°C) and a small glass funnel are also mounted
in holes drilled through the stopper. Both wires, the
soldered faces of the electrodes, and the bottom of the
stopper are insulated by means of an epoxy resin, com-
mercially available in paste form. The cell constant
has been determined to be 1.28 using a standardized
0.01000M KC1 solution.
The Reaction
A reaction was sought which would be sufficiently
swift so that a number of determinations could be
made in a single laboratory period, yet slow enough
to enable the student to obtain quantitative results
from his data. A reaction which meets these require-
ments is the decomposition of acetic anhydride in a
hydroxylic solvent. The reaction is quite rapid in
pure water, whereas in a less polar solvent, for example
in alcohol, the rate decreases more than one hundred
fold. Therefore, a small quantity of alcohol added to
the reactant will retard the rate to a practical level as
well as promote complete dissolution of the anhydride
i r ~water.
Acetic anhydride decomposes in water according to
the following overall reaction:
(CH,CO),O + H20 - 2CHsCOOH (4)
I I i i I I The acetic acid formed immediately undergoes an
IOR, ionization st,ep
CHICOOH + H 2 0 = C H S O O - + HaO+ (5)
The hydronium ion thus produced bccomes the primary
contributor to electrical conductivity in the solution.
Therefore, the progress of the reaction can be followed
by observing the conductance change of the solution
due to the increase in the [H,O+]. I t has been sug-
gested that the rat,e controlling step involves the
Figure 3. A photograph of the instrument and ossocioted equipment.
Volume 39, Number 3, Morch 1962 / 141
severance of a carbon-oxygen bond in the anhydride
molecule, followed by rapid combination with the
hydroxylic solvent (4, 5, 9). The reaction mechanism
is thus represented as:
HlO
(CHaC0)zO +CHaCOO-
CH&OO-
slow
+ CHaCO+ + H1O - fast
+ CHICO+
ZCHSOOH
(6)
(7)
If the [H,O] is maintained large compared to the an-
hydride concentration, to be written as [Ac20], then
the reaction approaches first order with respect to the
[AcZO]. Therefore, the rate equation becomes:
where k is the first order rate constant. Integrating
between the limits, initial anhydride concentration
[AcpOIoat time zero, and [Ac20]at any time later,
Since the solution resistance R, is a function of the
hydronium ion concentration,
Here Ro represents the initial solution resistance and
+, a constant, is a function of the ionic mobilities.
From equation (5) the ionization constant for acetic
acid is approximately:
Solving equation (11) for [H30+]and substituting back
in equation (10)
From equation (4) :
[AcOH] = 2 [[AsOl0 - [Ar20]I (13)
Therefore equation (12) may be rewritten as
The terminal resistance of the solut,ionR ,is
The constant 4 may be eliminated between equations
(14) and (15),
Solving equation (16) for the concentration terms
Therefore the rate equation in terms of resistances may
be obtained by subst,ituting for the concentration from
equation (14) back into equation (9) and rearranging.
Where B = [(R,/R=)-112
142 1 Journal of Chemical Education
To determine the initial solution resistance Ro a
plot of R. versus time must be extrapolated back to
zero time. I t often will be found however, that Ro is
much greater than R m , hence equation (18) can be
further modified under these circumstances, eliminating
R~entirely,to yield
From equation (18) or (19) the student may obtain the
rate constant k as the absolute value of the slope of the
straight line plot of the left member versus time.
For the sophisticated student with some background
in physical chemistry, the foregoing analysis offers
little more than a routine challenge. He should be
able to handle the normal laboratory techniques and
the mathematical interpretation with a minimum of
direction. I n the course of a laboratory period such a
student can make a number of determinations to study
the effect of such parameters as initial anhydride
concentration and temperature on the rate of reaction.
From these latter runs, a graph of the Arrhenius equa-
tion would be used to evaluate the activation energy.
On the other hand, for a beginning student whose
knowledge of physical chemistry and whose math-
ematical acumen is limited, such an approach might
foster more confusion than insight. Therefore, in
order for this student to derive the maximum benefit
from the experiment, an instrument calibrated t o read
concentration values directly (Fig. 4) would be more
suitable. I n this case, however, the integrated rate
expression, equation (9), would be employed to de-
termine the rate constant:
Figure 4. Calibration curves of acetic acid concentration as o fundion of
meter reading far on input voltage of 50 v ac.
Insfrumenf Calibration
In order to calibrate the instrument in terms of
concentration, it is first necessary t o establish a graph
of temperature versus meter reading for a series of
standardized acetic acid solutions ranging in composi- The last column indicates the length of time for which
tion from about 1.000 M to 0.005 M. Approximately each reaction was followed.
100 ml of each solution is required.
To exactly 50 ml of each acetic acid sampl? add 1.00 Table 1: A Typical Set of Runs
ml of absolute alcohol. This quantity of alcohol,
which aids the dissolution of the anhydride in water a t [Ae201 Temp.
Run AGO (moles/ HzO avg. Time
the onset of the reaction, will require that a concentra- no. (ml) liter) (ml) ("C) (min)
tion correction be made for each sample. Using a
water bath to adjust the solution temperatures (ice
water a t the lower temperatures), obtain meter readings
at about 8'C intervals from 10 to 50°C for all of the
solutions. It would be best to check each reading
twice, once as the solution temperature rises, and again
as it descends through each temperature point. Swirl Results
the solutions gently as the readings are taken to be sure
that thermal equilibrium has been established. From Values of the reaction rate constant can he deter-
the data a series of constant composition curves are mined graphically using either equation (9) or (19).
prepared of temperature versus meter reading. Draw The plotted experimental data are shown in Figure 5.
smooth curves through the plotted points. Using t,he
data of this primary graph, the concent,ration-meter
reading calibration is constructed as a crossplot of the
data for temperature intervals of 5'C, as indicated in
Figure 4. From this graph and equation (13), the
experimental data are converted to read in terms of
anhydride concentrations for use with the integrated
rate expression, equation (9).
Subsequent calibrations for a number of instruments
are prepared using this data as a reference. The only
other information required is an accurate determination
of the cell constant for each instrument. Thus, from
the relationship

(where R is the solution resistance, K is the ccll con-

stant, and subscripts u and c represent the uncalibrated
and calihratedi nstruments, respectively) additional
calibrations can be determined.

The Experiment
When the bath and solvent have been adjusted to TIME, MIN.
the desired temperature, 1.00 ml of absolute alcohol is
Figure 5. A sample plot of experimental data for the determination of the
added to a measured quantity of anhydride in a 100-ml rate constant urine equation (9).
beaker. With the electrodes firmly in place and the
whole assembly supported by the ringstand, the beaker These calculated k's are compared with the experi-
(cell) is submerged in the bath about half way. Then mental values of Banks, et al., (1) in Table 2, for the
a pre-determined amount of distilled water is added to
decomposition of acetic anhydride in aqueous solution.
the reactant through the funnel. Commence timing As can be seen, the overall agreement between the
when about half of the solvent has been charged. Tem- computed k values for this report are well within
peratures and meter readings should be taken at 30- experimental tolerances. Those obtained from equa-
second intervals or oftener for the first two minutes
tion (15) average about 6% greater than the k's from
and every minute or two thereafter. Temperature equation (6). Therefore, the assumption that the
control can be maintained to within a few tenths of a
ratio R = / R o is negligible, made in the derivation of
degree by raising or lowering the beaker and period-
ically swirling the solution. The reaction should be
followed until about 15 readings have been recorded, Table 2: A Comparison of the Resulfs
or for approximately 10 to 20 min. depending on the Temp.
reaction temperature. Since the reaction will be in- Run avg. k Calculated (min.-1) k Lit.*
complete a t this time, set the solution aside for an no. ('C) Em. ( 9 ) Em. (19) (min-1)
additional 45 min. before obtaining a terminal reading.
In Table 1 are shown five typical runs that were per-
formed in a single laboratory period; these runs may
he used as a guide for the design of other experiments.
I n all cases the total reactant volume was 51.0 ml.
Volume 39, Number 3, March 1962 1 143
equation (Is), appears justified. Literature values on
the other hand are generally 10% to 15% larger in most
cases. This is to be expected however, for in the runs
presented here, the introduction of a small quantity of
alcohol with the reactant would tend to reduce the
reaction rate by a measurable amount.
The activation energy for the reaction is 11,400
cal/mole as calculated from the slope of the Arrhenius
plot (In k versus l/T). This compares favorably with
the values obtained by Wilhelm and Cleland ( l o ) ,and
Banks, et al. (1).
. Although the conductivity measuring instrument
described in this paper has been designed primarily for
the decomposition of acetic anhydride reaction, it can
with suitable modification be used t o follow many
other reactions of this general nature. Two other reac-
tions well adapted to this method are the saponification
of ct,hyl acetate (3) and the hydrolysis of tertiary bulyl
chloride (3).
Acknowledgment
The author wishes to express his appreciation to
144 / Journal of Chemical Educofion
Professors Neustadt and Leydorf of the Science De-
partment of the U. S. Naval Academy for their help
with the circuitry.
Literature Cited
(1) BANKS,E. N., ET AL.,Can. J . Res., 28B, 669 (1950).
(2) CAESICK,J. P. AND PATTERSON,A,, JR.,J. CHEM.EDUC.,
37,242 (1960).
(3) DANIELS,3. M., ET AL., "Experimental Physical Chem-
istry," 5th ed., McGraw-Hill Book Co., Inc., New York,
1956, p. 130.
(4)GOLD,V., AND JEFFERSON,E. O., J . c h m . Soc., 1409,
1416 (1953).
( 5 ) HINE, J., "Physieal Organic Chemistry," McGrmv-Hill
Book Co., Inc., New York, 1956, p. 301.
(6) MAEON,S. F., AND LAMER,J., J . Am. Chem. Soc., 61, 692
(1939).
(7) ORTON,K.J . P. AND JONES, M., J . C h a . Soc., 101, 1708
11912).
(8) h he ~ a d i oAmatuer's Handbook," 1946 ed., The Ameri-
can Radio Relay League, West Hartford, Conn., 1946,
p. 183.
(9) RIVEIT, A. C. D. AND SIDGWICK,N. V., J . Chern. Soc.,
97,732 (1910).
(10) WILAELM, R. H. AND CLELAND, F. A., A. I. Ch. E. Jow.,
2,403 (1956).