CHM172.

1 H78 - Physical Chemistry Lab September 15, 2023

MYRA JANE S. CABO

ACTIVITY 2 – DATA INTERPRETATION

I. Determining the order of reactions

Following the provided instructions, the assigned task for the student involved conducting experiments to
determine the reaction's order, specifically investigating whether it conforms to zero, first, or second-order
kinetics. This study primarily focuses on examining the reaction that involves the oxidation of ethanol by
dichromate. Through the process of oxidizing ethanol with dichromate in the presence of a substantial excess
of alcohol and acid, a testing dataset for zero, first, or second-order reactions was generated. The dataset
required for generating the plot is already provided which is shown in the Excel spreadsheet. By graphing
[HCrO4-] against time for zero-order, ln[HCrO4-] against time for first-order, and 1/[HCrO4-] against time
for second-order, it becomes possible to construct straight-line graphs that serve as a means to confirm the
reaction's order. Figures 1, 2, and 3 below display the data plots for [HCrO4-], ln[HCrO4-], and 1/[HCrO4-]
over time, which will be used for comparison to ascertain the reaction's order.

0.008
0.007
0.006 y = -6E-05x + 0.0067
0.005 R² = 0.9592
[HCrO4-]

0.004
0.003
0.002
0.001
0
0 20 40 60 80 100 120
TIme/min

Figure 1. Plot of Zero Order

0
0 20 40 60 80 100 120
-1
-2
ln[HCrO4-]

-3 y = -0.015x - 4.9079
R² = 0.9988
-4
-5
-6
-7
TIme/min

Figure2. Plot of First Order

 700
600
y = 4.593x + 90.166
500 R² = 0.9575

1/[HCrO4-]
400
300
200
100
0
0 20 40 60 80 100 120
TIme/min

Figure3. Plot of Second Order

Upon comparing the linearity of the three figures above, it became evident Figure 2 demonstrated the most
precise linear relationship among them, as indicated by an R-squared (R²) value of 0.9988. This is in contrast to
Figure 1 and Figure 3, which displayed R² values of 0.9592 and 0.9575. Hence, based on linearity evaluation, it
can be concluded that the chemical reaction involving HCrO4- is best described as a first-order reaction.

II. Determining missing data for a 1st order reaction

The primary objective of this exercise is to ascertain the missing final reading, often referred to as the 'infinity
reading,' within a dataset acquired during the hydrolysis of methyl acetate in a 1 M HCl solution. The chemical
reaction being studied can be described by the following equation:
CH3COOCH3 + H2O → CH3COOH + CH3OH

Table 1. . Estimation of Vinf derived from a graph plotting V vs. t

Test for Vinf
Vinf Sum of d2
35 0.294733
38 0.090476
40 0.039647
42 0.019207
43 0.015575
44 0.01481
45 0.016147

Table 1 showcases an approximation of the "infinity reading" obtained from a graph that plots V against t. The
graph covers a range of values starting from an initial point of 35 cm3 and extending to 45 cm3. The detailed
calculations for the values listed in this table, which were derived by summing d2, can be located in the
accompanying Excel document.
 Based on Table 1, it is evident that the lowest d2 values for Vinf can be observed at 43 and 44. This indicates
that the precise Vinf value is probably situated within this range. Consequently, an approximate estimation for
the infinity reading of the reaction was determined between 43 and 44, as illustrated in Table 2 and plotted in
Figure 4.

Table2. Evaluation of Vinf values between 43 and 45

Vinf Sum of d2
43.4 0.014973
43.5 0.014888
43.6 0.014826
43.7 0.014788
43.8 0.014774
43.9 0.014781

0.015

0.01495

0.0149
∑d2

0.01485

0.0148

0.01475
43.3 43.4 43.5 43.6 43.7 43.8 43.9 44
Vinf

Figure4. Plot of Σd2 vs. Vinf

After conducting critical experimental calculations, as demonstrated in Table 1 and Figure 4, the value Vinf
43.8cm³ shows the smallest sum of d2, suggesting a deviation of 0.45% from the theoretical value of 43.6cm³.
The slight deviation of the experimental value from the theoretical value comes from the calculations that are not
rounded off. It was established that the minimum sum of squared differences (Σd²) for Vinf was achieved at 43.6,
with a calculated value of 0.014826. As a result, the anticipated measurement for the reaction's infinity reading
was set at 43.6 cm³. Therefore, Table 3 presents the recorded values pertaining to the missing data for the first-
order reaction.
Table3. Reported values on the missing data for the first order reaction
REPORTED VALUES
Vinf V0 k Average Σd2
43.6 cm³ 25.8 cm³ 9.02 x 10-5 0.0148

The values are as follows: Vinf = 43.6cm3, V0 = 25.8cm3, the average rate constant (k) = 9.02 x 10-5 min-1, and
the sum of d2 = 0.01482047.

III. Simultaneous decay of two radio-isotopes

In this section of the exercise, the students investigate the simultaneous decay of two radioisotopes. Radioactive
decay is a stochastic process in which the population of radioactive nuclei decreases with time. Consequently,
each radioactive isotope adheres to a first-order reaction.
Table 4 displays the total activity in counts per minute that were determined for the simultaneous activity of two
radio-isotopes.

Table 4. Data for the simultaneous activity of two radio-isotopes

Time Activity
ln(activity)
(min) (counts/min)
0 140 4.9416
1 117 4.7622
2 98.7 4.5921
3 84.3 4.4344
4 73 4.2905
5 63.9 4.1573
6 56.7 4.0378
7 50.9 3.9299
8 46.3 3.8351
9 42.5 3.7495
10 39.4 3.6738
12 34.6 3.5439
14 31.2 3.4404
16 28.6 3.3534
18 26.6 3.2809
20 24.9 3.2149
25 21.6 3.0727
30 18.9 2.9392
35 16.7 2.8154
40 14.7 2.68785
50 11.5 2.44235
60 8.92 2.1883
70 6.95 1.93874
80 5.41 1.68825
90 4.22 1.43984
100 3.28 1.18784
The data related to the simultaneous decay of two radioisotopes is presented in Table 4. The decay process
follows first-order reaction kinetics, which implies that a linear relationship can be observed by plotting the
natural logarithm of the total activity against time. In this graph, one would anticipate a negative slope,
representing the rate constant (-k).

6 A+B
5
4
ln(activity)

3
2
1
0
0 20 40 time 60 80 100
Figure 5. The overall plot of activity against time

The procedure begins with an initial step of plotting the natural logarithm of the total activity against time, as
demonstrated in Figure 5. This graph distinctly shows that the radioisotope with a rapid decay rate undergoes
substantial decomposition during the early phases of the experiment. As time progresses, the only observable
activity originates from the slowly decaying nuclide, B. Therefore, by constructing a new graph, as depicted in
Figure 6, during the later time interval of 40 to 100 minutes, it can be confidently asserted that this graph will
exclusively depict the activity of B.

Acivity of B
3
2.5
2
ln (Activity)

1.5
1
0.5 y = -0.025x + 3.6903
R² = 1
0
0 20 40 60 80 100 120
Time (min.)

Figure6. The plot of activity B against time

Figure 6 provides a detailed representation of the activities of B within a specific time frame, ranging from 40 to
100 minutes. The graph displays a linear relationship, evident from the equation y = -0.025x + 3.6903 and an R²
value of 1, indicating a perfect fit to the data. Consequently, the rate constant for B was computed to be 0.025.
Furthermore, [A]0 was established at 40.05686221 counts/min.
By thoroughly analyzing the graph and utilizing the line equation representing B's activity, it becomes possible
to determine the initial activity (A0) of B. This can be accomplished by calculating A0 of B as the exponential
function of the natural logarithm of the y-intercept. Additionally, the decay rate can be inferred from the slope of
the linear equation. Subsequently, these acquired values can be employed for further calculations to determine
the activity of A, as illustrated in the accompanying Excel spreadsheet.

Activity of A
5
4.5
4 y = -0.2524x + 4.6136
3.5 R² = 1
3
2.5
2
1.5
1
0.5
0
0 5 10 15 20

Figure 7. Plot of activity A against time

Figure 7 illustrates the time-dependent relationship between Activity A and time, spanning from 0 to 18
minutes. This relationship is derived from the calculated natural logarithm of its activity, as presented in the
Excel spreadsheet. The graph exhibits a clear linear pattern, evidenced by the linear equation: y = -0.254x +
4.6136, and a substantial R-squared value of 1, indicating a strong linear correlation. The rate constant for A
was determined to be 0.2524. This illustrates that by analyzing the concurrent activity of two radioisotopes
and plotting the data on a logarithmic scale, it becomes possible to calculate the rate constants (kA and kB) for
each isotope. This method provides a means to gain insights into the decay kinetics of the mixture and
enhances our understanding of the behavior of the radioactive isotopes involved.
Table5. Reported Values for Activity A and B
Activity: k (rate A0 Line Equation
constant)
A 0.2524 100.8465 y = -0.2524x +
4.6136
B 0.025 40.056862 y = -0.025x +
21 3.6903

In Table 5, you can find the recorded values for the activities of A and B.