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Identification of Factors Affecting Chemical

Kinetics Through Observation of [S2O82-] and [I-]


in Varied Systems
C. M. M. E. Tan1
1
Institute of Chemistry, College of Science
University of the Philippines, Diliman, Quezon City, Philippines
Date Performed: January 30, 2019
Date Submitted: February 8, 2019

Abstract
The kinetics of the reaction between S2O82- and I- was observed in and through various
systems with differing concentrations of reactants, differing temperatures, and addition of a
catalyst. This was done through the preparation of five set-ups with varying concentrations of
the five reactants. The effect of temperature was observed through submersion in a warm
water bath and in an ice bath. The effect of a catalyst was observed through the addition of
0.01M CuSO4. The resulting rate law of the reaction was rate = k [S2O82] [I-] with a rate
constant of 0.006 M-1s-1. The pertinent activation energy and Arrhenius constant are 58.55 kJ
mol-1 and 8.77x107, respectively. It was concluded that an increase in the concentration of the
reactants, increase in temperature, and the presence of a catalyst increase the rate of the
reaction. The study recommends the use of varied statistical tools such as pool standard
deviation.

1. Introduction This process is done in lieu of testing for the


The rate at which a reaction is known to concentration of the system at certain time
move forward is described as the speed at intervals, as it is presently an inefficient
which a product is formed or the speed at method for such laboratory setting. The
which a reactant is consumed [1]. With this initial rates method requires maintaining the
said, the rate of a chemical reaction is concentration of one reactant to be constant,
majorly affected by a number of factors. while varying the concentration of the other
These factors are primarily identified as the and measuring the rate at each varied
concentration of reactants, the temperature system.
of the system, and the presence of a catalyst In addition to the concentrations of
in the system. the reagents, another factor affecting rate of
The experiment conducted observes the reaction is the nature of the reactants. A
chemical reaction between the iodine anion theoretical model relevant to this is the
I-, and the persulfate cation S2O82-. The collision theory. A branch of this concept
reaction moves forward as follows: most relevant with respect to chemical
S2O82- + 2I- à 2SO42- + I2 kinetics is collision density, which is defined
The primary trial in which this reaction is by the number of molecular collisions per
scrutinized is under changing concentrations unit volume per unit time [2]. Collision
of the reactants. In doing so, the orders of theory states that not all molecular collisions
the reaction of S2O82- and I- respectively can will constantly result in a reaction, instead, a
be determined through the initial rates fast-moving particle is required. In order for
method. Through this process, the rate law this reaction to move forward, molecules
of the reaction is given by: must exert a certain amount of activation
rate = k[S2O82]x[I-]y energy, which is the utmost minimum
kinetic energy for a chemical reaction to
occur. For this experiment in particular, the identify the effect of temperature on the
activation energy of the pertinent reaction reaction rate and compute for the
was determined through subjecting the corresponding Arrhenius constant and
system in various temperatures. An increase activation energy, and lastly, observer the
in temperature allows for more successful effect of a catalyst to the reaction rate.
collisions and therefore higher particle
movement. The effect of the change in
temperature upon the rate of the reaction is II. Methodology
described by the Arrhenius equation, such The preliminary course of the
that: procedure involves the preparation of
𝐸! solutions. 250mL of each reagent was
𝑙𝑛𝑘 = 𝑙𝑛𝐴 −   prepared, the concentrations of which are
𝑅𝑇
In this equation, A is the Arrhenius constant, 0.2M KI, 0.2M KCl, 0.1M K2S2O8, 0.1M
Ea is the activation energy, T is the K2SO4, and 4.0mM Na2S2O3. 20mL of 1%
temperature in Kelvin, and R is the universal (w/v) fresh starch solution was also prepared
gas constant. Having experimental rate by means of moistening 0.2g of starch with
constants and reaction temperatures allows water until it formed a smooth paste. This
for the determination of the activation mixture was poured slowly into a 20mL
energy and the Arrhenius constant. Another beaker of boiling water, which was kept at a
means of lowering the activation energy constant temperature between 90oC and
aside from increasing the temperature is the 100oC. For the system involving a catalyst,
introduction of a catalyst to the system. A 50mL of 0.01M CuSO4 was also prepared.
catalyst steers the reaction towards a path of The effect of persulfate and iodide
lower activation energy, and thus expedites concentrations on the rate of the reaction
the rate of the reaction [2]. While it was firstly measured. Five set-ups of
participates in the reaction, it does not differing concentrations were prepared.
undergo reduction or consumption and thus
does not appear in the overall chemical Table 2.1 Set-ups for the effect of persulfate
equation. and iodide concentrations on reaction rate.
For the experiment presently Beaker B (+ 3 drops of
Beaker A
fresh starch)
undertaken, the rate at which the reaction is Run
0.2M 0.2M 0.1M 0.1M 4.0mM
measured is based upon the rate of I2 KI KCL K2S2O8 K2SO4 Na2S2O3
formation. The deep blue complex formed as 1 10.0 0.0 5.0 5.0 5.0
starch is added represents the presence of I2.
This series of reactions is otherwise known 2 5.0 5.0 5.0 5.0 5.0
as the Iodine Clock. The series of reactions 3 2.5 7.5 5.0 5.0 5.0
is as follows:
4 5.0 5.0 7.5 2.5 5.0
2I-(aq) + S2O82-(aq) à I2(aq) + 2SO42-(aq)
2S2O32-(aq) + I2(aq) à S4O62-(aq) + 2I-(aq) 5 5.0 5.0 10.0 0.0 5.0
I2(aq) + starch à deep blue complex The contents of Beaker A were
As the S2O32- is fully consumed, I2 begins to poured into Beaker B. Upon combination,
form. Thus, knowing the rate at which S2O32- the reaction was immediately timed up until
is consumed and assuming that S2O32-and I2 the mixture presented the slightest
are stoichiometrically equal, the rate of indications of a blue hue. The temperature of
formation of I2 can be computed [3]. the reaction was also taken into account.
The experiment at hand sought to Following this, the effect of the
observe and describe the kinetics of the presence of temperature on the reaction rate
reaction, utilize the initial rate method in was also observed. An additional 2 set-ups
determining the rate law of the reaction and of run 2 was prepared, henceforth labeled set
in turns, the rate order of the reactants, 2 and set 3, respectively. Beakers A and B of
set 2 was treated in a water bath at around 1
ln 𝑘  𝑣𝑠.
50oC (40oC – 60oC). The contents of both 𝑇
beakers were combined, and the reaction The independent variable, T, is the
was timed until the mixture began to turn reaction temperature in Kelvin, while k is the
blue. Beakers A and B of set 3, on the other calculated rate constant of the particular
hand, was cooled in an ice bath. At 5oC (0oC reaction. The slope of the plotted line
– 10oC), the contents of Beaker A were multiplied to R represents the activation
poured into Beaker B. The reaction was energy of the reaction.
timed until the mixture appeared to have a
blue hue. III. Results and Discussion
The last experimentation done was [S2O82- [S2O32- Reaction Rate, M
with respect to the effect of a catalyst on the Run [I-]
] ] time, s s-1
reaction rate. An additional set-up of run 2 9.75x10-
1 0.02 0.08 0.0008 41.01 6
was prepared, duly labeled set 4. 3.75x10-
Immediately after combining the contents of 2 0.02 0.04 0.0008 106.74 6

Beaker A to B, 4 drops of 0.01M CuSO4 was 3 0.02 0.02 0.0008 162.47


2.46x10-
6
added, and the time that lapsed until a blue
7.04x10-
color was observed was recorded. 4 0.03 0.04 0.0008 56.80 6

Residual and resulting solutions were 5 0.04 0.04 0.0008 33.84


1.18x10-
5
disposed into appropriate waste jars.
Solutions containing Cu(II) was transferred Table 3.1 Treated data for determining the
to the inorganic waste jar, whereas all other effect of reactant concentration on reaction
solutions were diluted with copious amounts rate.
of running water and disposed into the sink. The rate of the reaction from Table
The treatment of data for the 3.1 is the quotient of the molarity of I2 and
experiment first involved determining the the reaction time in seconds from when the
best fit line of the natural log of the mixture was seen to present a blue hue. The
concentration of a particular reactant and the molarity of I2 was calculated based on the
natural log of its respective rate. For molarity of [S2O32-]. As was
instance, the coordinates of the best fit line abovementioned, the rate of formation of I2
of the S2O82- reactant would be: is theoretically equal to rate at which [S2O32-]
ln 𝑟𝑎𝑡𝑒  𝑣𝑠. ln[S! O!! was consumed. Thus, the rate of the reaction
! ]
In this facet, the independent would be calculated based on:
variable, [S2O82-] is the molarity of the 0.0004𝑀  𝐼!
𝑟𝑎𝑡𝑒 =  
reagent in the solution with the total volume 𝑇  (𝑠)
of 25mL, whereas the dependent variable is Preliminary discussion of the treated
the rate at which the reactant was consumed. data shows that there is an inversely
The same applied to the [I-] reagent. For the proportional relationship between the
graph of the line of [S2O82-], only values concentration of [I-] and the rate of the
wherein [I-] was constant were considered, reaction, as evidenced by set-ups 1, 2, and 3
whereas only values where [S2O82] was where [S2O82-] is constant. The same is true
constant were used for the graph of [I-]. The for the relationship between [S2O82-] and the
slope of each line represents the rate order of rate of the reaction, wherein reaction time
the particular reactant. increased as the concentration of this reagent
The data treatment for the gathered decreased. This is seen in runs 2, 4, and 5
information regarding the effect of wherein the concentration of [I-] remains
temperature involved a similar process, constant.
wherein the natural log of k was plotted
against the reciprocal of T, such that:
Graph 3.1 The graph of the best fit line of Graph 3.2 The plotted best fit line of ln rate
ln rate vs. ln [S2O82-]. vs. [I-].
The best fit line of ln rate vs. ln The best fit line of ln rate vs. [I-]
[S2O82] has an equation of: presents an equation: presents an equation:
y = 0.61x + 3.68 r2 = 0.99 y = 0.96x + 8.59 r2 = 0.952
Following the principle that slope m With respect to the premise
is equal to the rate order of the reactant, it aforementioned, the rate order of [I-] is 0.96,
can be derived from the equation that the or approximately 1. Cognizant with the
rate order of [S2O82] is 0.61 or approximately experimental rate order of [S2O82], it puts
1. This indicates that the consumption of forward that the degradation of [I-] as a
[S2O82] as a reactant alone is a first order reactant is a first order reaction. The r2 of the
reaction. equation is similarly high to that of the
Based on the r2 of the equation, the previous equation, with an accounted 95%
regression accounts for 99% variance, variance, asserting that the data are strongly
indicating that the data tightly fits the model. correlated.
This presents that the concentration of The rate constant of the reaction was
[S2O82] and the rate of the reaction are highly computed for by using the rate law equation:
correlated. rate = k [S2O82] [I-]
Having previously identified the rate orders
of the reactants by means of the initial rates
method, it only leaves the constant k to be
the unknown value. By acquiring the mean
value of k from all 5 set-ups, the computed
rate constant is:
k = 0.006 M-1s-1
With this, the rate law can now be written
as:
rate = k [S2O82] [I-]
rate = 0.006 M-1s-1 [S2O82] [I-]

The data surmised from the


experiment on the effect of temperature and
catalyst on reaction rate follows the
concentrations of run 2 from the previous
section, wherein [S2O82] = 0.02, [I-] = 0.04, y = -7042.1x + 18.29 r2 = 0.99
and [S2O32-] = 0.0008. Recalling the Arrhenius equation
aforementioned:
Temperature, Reaction Rate, M Rate 𝐸!
Set
K time, s s-1 constant 𝑙𝑛𝑘 = 𝑙𝑛𝐴 −  
𝑅𝑇
1 297.15 106.74 3.75x10-6 4.69x10-3 It can be seen that this equation closely
2 335.15 7.69 5.20x10-5 6.50x10-2
3 283.00 378 1.06x10-6 1.33x10-3
follows the y = mx + b formula. It can be
4 297.15 21.23 1.88x10-5 2.35x10-2 derived that:
Table 3.2 Raw and treated data collated 𝐸!
𝑚𝑥 =  
from observing the effect of temperature and 𝑅𝑇
catalyst on the reaction rate. Thus:
The same computation on acquiring 𝐸! 1
−7042.1𝑥 =   − ×
the rate constant following the rate law was 𝑅 𝑇
done in order to calculate the rate constant of Computing for the quotient of m and the
each set. Through the superficial data, it is universal as constant R, it is seen that the
evidenced that temperature and reaction time activation energy of the reaction is:
have an inverse relationship such that an Ea = 58.55 kJ mol-1
increase in temperature dictates a decrease in In turn, it can be derived that:
reaction time. In turn, the increase in 18.29 = lnA
temperature promotes a higher rate of And, by reorganizing the expression into the
reaction. This is further modeled by the corresponding natural logarithm, the
equation of the line of the plot: Arrhenius constant is equal to:
1 A = 8.77 x 107
ln 𝑘  𝑣𝑠. With further research, the approximated
𝑇
activation energy of the reaction is
theoretically 51.80 kj mol-1 [4]. This being the
case, the computed %error is:
58.55 − 51.80
%!""#" =  ×  100
51.80
= 13.03%
Seeing that 13.03% is largely outside the 5%
window of error, it can be deduced that a
great error has been committed in some area
of the experiment.
The theoretical value of the
Arrhenius constant is seemingly disputed in
related literature, and no common value has
been identified since it is a reaction-related
constant. However, following the same
values for the theoretical value of the
activation energy, it is approximated that the
Graph 3.3 The best fit line of lnk vs. T-1. Arrhenius constant of this reaction is:
The proximity of the line to the y- A = 5.81 x 106
axis is due to the x values T-1 closely With this, the percent error of the
approaching 0. While this does not indicate experimentally acquired A value would
any significant implications regarding the result to:
linear regression of the two variables, it 8.77×10! − 5.81×10!
%!""#" =  ×  100
should be duly pointed out, as it appears that 5.81×10!
the line is indistinguishable. = 1409%
The equation of the line is:
Based on the %error of the Arrhenius value. A tool such as pooled standard
constant, it can be assumed that a large error deviation is suggested so that the dispersion
has been committed. of data can also be identified.
The errors incurred during the
experiment are firstly attributed to V. References
instrumental errors. In the case of wrongly [1] In General Chemistry II Laboratory
calibrated thermometers and timers, the Manual; Institute of Chemistry, University
measurement of time and temperature could of the Philippines Diliman: Quezon City,
have been greatly affected, and in turn, 2018; pp 5–7.
affected the calculated values. Another [2] Petrucci, R. H.; Herring, F. G.; Madura,
source of error is observational. The J.; Bissonnette, C. General Chemistry:
experiment was executed as a laboratory Principles and Modern Applications, 10th
class, hence, the interpretation of bluish hue, ed.; Prentice Hall: Boston, 2016.
for instance, could have been not standard, [3] Altig, J. Determination of the Rate
and thus has affected the measurement of Constant for an Iodine Clock Reaction.
time of the reaction. https://infohost.nmt.edu/~jaltig/ClockRxnKi
netics.pdf (accessed Feb 7, 2019).
IV. Conclusion and [4] Chanatry, J. Chemical Kinetics: The
Recommendation Iodine-Clock Reaction.
The reaction between [S2O82] and [I-] http://classes.colgate.edu/jchanatry/chem102
is an overall second order reaction, such that /exp16calcsw.pdf (accessed Feb 7, 2019).
an increase in the concentration of the
reactants will merit an increase in the rate of
the reaction. Other factors that will increase
the rate of the reaction are an increase in the
reaction temperature and an addition of a
catalyst to the system.
All objectives of the experiment
were completed, having identified the rate
law of the reaction to be rate = k [S2O82] [I-].
The calculated activation energy was Ea =
58.55 kj mol-1 and the Arrhenius constant
was A = 8.77 x 107.
Having observed the various possible
sources of error in the experiment, it is
advisable to modify some areas of the
methodology in order to ensure the most
accurate obtained values possible. Firstly,
the observer for the reaction indicator, the
blue complex, should be the same for all
subsequent runs and sets. In addition, the
timers or stopwatches used in timing the
reaction should all be standardized and
similarly calibrated. Time is an important
variable in the experiment, and its accuracy
is detrimental to the results of the research.
The study recommends the use of a
more reliable statistical tool rather than
linear regression and its accompanying r2