Departament de Química Física i Inorgànica

Physical Chemistry area

PHYSICAL CHEMISTRY
LABORATORY

Equilibrium and kinetics block

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

CONTENTS

EQUILIBRIUM AND KINETICS BLOCK

Colorimetry: determination of an equilibrium constant………………………………3
Kinetic study of the reaction between iodide and persulfate……….…….…….……12
Determination by conductimetry of the rate of saponification of ethyl acetate……...16
Annex: Results and errors……………………………………………………………20

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

COLORIMETRY: DETERMINATION OF AN EQUILIBRIUM CONSTANT

GOALS
1. To determine the thermodynamic equilibrium constant of the complexation reaction:
SCN– + Fe3+ ⇄ Fe(SCN)2+
2. To apply the scientific method.
3. To apply an iterative method.
4. To do the calculations in a numeric spreadsheet that could be used for different input data
sets.
5. To analyse errors and learn from them.

INTRODUCTION
Equilibrium constant
The thermodynamic equilibrium constant of a chemical reaction at a given temperature, K(T) is
unique and is defined as:

𝝂 𝝂 𝝂
𝑲(𝑻) = ( 𝒂𝒊 𝒊 = ( 𝜸𝒊 𝒊 𝒄𝒊 𝒊 = 𝑲𝜸 𝑲𝒄
𝒊 𝒊

Experimentally, concentrations at equilibrium can be measured (Kc). For the studied reaction:
SCN– + Fe3+ ⇄ Fe(SCN)2+
t=0 a b –
t = eq (a – x) (b – x) x

where a and b are the initial concentrations of SCN– and Fe3+, respectively, and x is the concentration
of complex at equilibrium. So,

𝒙
𝑲𝒄 =
(𝒂 − 𝒙)(𝒃 − 𝒙)

For the studied reaction, the experimental determination of 𝐾% implies the experimental
determination of x (by colorimetry) and the initial concentrations of a and b (where dilution has to be
taken into account).
If the reaction involves ionic species, activity coefficients are usually rather different from unity
(since the interactions between ions are far from being ideal). Therefore, we must consider 𝐾& :

𝜸𝒙 𝜸 𝟐#
𝑲𝜸 = = 𝐅𝐞𝐒𝐂𝐍
𝜸𝒂 𝜸𝒃 𝜸𝐒𝐂𝐍$ 𝜸𝐅𝐞𝟑#

Activity coefficients, in turn, depend on the ionic strength, I:

1 1
𝐼= 3 𝑍/0 𝑚/ = 3 𝑍/0 𝑐/
2 2𝜌
/ /

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

which is determined from charges, Zi, and molalities, mi, of ALL the ionic species present (either they
participate in the reaction or not). Molalities can be approximated to concentrations, ci, from the
solution density, r ≈ 1.02 g/mL for the studied system. The relationship between the activity
coefficient, gi, and the ionic strength of a species is given by the Debye-Hückel limiting law at low
ionic strength (I < 0.01 m):

𝑙𝑜𝑔 𝛾/ = −𝐴=𝑍/0 =√𝐼

where A depends on temperature and the solvent (A = 0.509 in aqueous solutions at 25oC). For larger
ionic strengths (I ≈ 0.1 m), the Debye-Hückel law can be applied:

√𝐼
𝑙𝑜𝑔 𝛾/ = −𝐴=𝑍/0 =
1 + √𝐼

Experimentally, it has been observed that gi firstly decreases with I, as predicted by the Debye-Hückel
law, but then it increases. This increase can be due to solvation of ions producing a decrease in the
amount of free solvent and, therefore, to an increase of the effective concentration of electrolyte.
There are laws that allow to calculate the activity coefficients for solutions with larger ionic strengths
(up to 3 m), but these require knowledge of the structure of ions in solution. An empirical equation
that does not need knowing of the structure of the solution but that takes into account these effects
(to some extent) is the Davies law:

√𝐼
𝑙𝑜𝑔 𝛾/ = −𝐴=𝑍/0 = @ − 0.30𝐼D
1 + √𝐼

It has been proven to be valid for our studied system (I ≥ 0.3 m). This is the law that we will apply
for the calculation of activity coefficients.
Note that, for a given reaction, K(T) depends on temperature only, whereas 𝐾% and 𝐾& depend on
temperature and ionic strength. If the ionic strength of a system varies, the activity coefficients do
and, thus, 𝐾& . Consequently, 𝐾% has to vary to keep K(T) constant.
In this experiment, K(T) will be determined at 25oC for 5 samples with different initial concentrations
of KSCN and Fe(NO3)3 (a and b, respectively), using a solution of nitric acid as solvent, that we will
mix to generate Fe(SCN)2+ (xm). The amount of Fe(SCN)2+ formed will depend, thus, on the initial
concentrations, temperature and ionic strength. This will be done for 5 samples to get the average
value of K(T).
Preparation of the 5 samples is carried out from different volumes of KSCN 0.002 M (a0) and
Fe(NO3)3 0.002 M (b0), prepared with HNO3 0.5 M (d0). Volumes of HNO3 0.5 M will be added to
have the same volume for all the samples.
Nitric acid plays a very important role:
• It is an acid, preventing the formation of iron hydroxides (Fe(OH)n), which are also reddish
in colour.
• It is an oxidant, keeping iron as Fe3+.
• It is a strong electrolyte, contributing to ionic strength.

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

In the samples, the concentration of acid is much larger than the other species at equilibrium.
Therefore, ionic strength is practically that generated by nitric acid (I ≈ 0.5 M). Since all samples
have the same concentration of nitric acid, all have approximately the same ionic strength. Then, 𝐾%
and 𝐾& must also be (approximately) constant for all samples.
The determination of the concentration of nitric acid is very important!

Determination of the concentration of Fe(SCN)2+

The product of this reaction, Fe(SCN)2+, presents a red-orange colour that absorbs radiation at a
wavelength of 450 nm, whereas the reactants are colourless. At a given wavelength it exists a linear
relationship between the concentration of the absorbing substance and the absorbance of the sample,
which is given by the Lambert-Beer law:

4
𝐼 = 𝐼1 · 1023% Abs = 𝑙𝑜𝑔 I 4&J = 𝜖𝑙𝑐

where Abs is the optical absorbance, I and I0 are the intensity of light transmitted and incident to the
sample, respectively, 𝜖 is the so-called extinction coefficient, l is the path of the light into the sample
and c is the concentration of the light-absorbing substance in the sample. So, we can determine the
concentration of the complex by a colorimetric technique if we find out the relationship between the
absorbance and its concentration. Such relationship can be obtained by a calibration line (or standard
line), which is determined with concentration standards of known concentration of the complex (xp),
for which absorbance is measured at 450 nm at 25oC. The data follow a straight line:

Abs = int + slope·x

Where x are the concentrations of complex and Abs are the measured absorbances for each
standard solution. Once the calibration line is determined, the concentration of complex of each
sample (xm) is determined from the absorbance of the sample, the y-intercept (int) and the slope of
the line (slope).
Preparation of standard solutions with known concentration requires knowing the value of the
equilibrium constant at 25oC, which is precisely the parameter to be found in this experience. How
can standard solutions be prepared with this unknown? A typical solution is to prepare the standards
so that we can suppose that equilibrium is fully displaced towards the formation of complex. This can
be accomplished if [SCN–] >> [Fe3+] or [Fe3+] >> [SCN–]. Considering that SCN– can form Fe(SCN)n
with n = 1, 2, 3, 4 and 5 (all reddish in colour), we will chose the last option. From here, we will call
c (not b) the concentration of Fe3+ of the standard solutions to stress that its concentration is much
larger than that of SCN–.

SCN– + Fe3+ ⇄ Fe(SCN)2+

t=0 a c (>>a) –
t = final (a – a) = 0 (c – a) a Fully displaced equilibrium

This will be the initial hypothesis: suppose fully displaced equilibrium in standard solutions.
Preparation of standard solutions is done from 1 mL of KSCN 0.002 M (a0) and 5 mL of Fe(NO3)3
0.2 M (c0), prepared with HNO3 0.5 M (d0). For each standard, we will add a different volume of

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

HNO3 0.5 M to get standards with the complex concentration. It is important to stress that for
standards, the ionic strength is basically given by nitric acid and Fe(NO3)3. Note that as the amount
of HNO3 added increases, the concentration of Fe(NO3)3 dilutes and, thus, the ionic strength
decreases.

VALIDATION OF THE INITIAL HYPOTHESIS:

Once the equilibrium constant has been determined from the initial hypothesis (fully displaced
equilibrium in standard solutions), we can validate this approximation (scientific method). In this
approximation, the concentration of complex in the standards is maximal and equal to the
concentration of SCN–, which is the limiting reactant (𝑥51 = 𝑎). We call it Iteration 0.
To carry out such validation we will use the mean value of K(T), 〈𝐾(𝑇)1 〉, to check if equilibrium
is fully displaced towards the formation of complex in all standards. The ionic strength of all standards
has to be determined, then get 𝐾& for every standard and with 〈𝐾(𝑇)1 〉 (valid at 25oC and for any
ionic strength) determine 𝐾% for every standard. From the initial concentrations and 𝐾% we can
determine the concentration of complex in each standard ( 𝑥56 ) assuming not fully displaced
equilibrium. We will compare the concentration values of complex in the standards considering fully
displaced equilibrium (𝑥51 = 𝑎) or not (𝑥56 ≤ 𝑎). Depending on the difference between 𝑥56 and 𝑥51 , if
it is significant or not, the initial hypothesis will be validated. You will observe a significant
difference. The process will be improved by learning from errors.
If there is a significant difference, equilibrium has to be considered in standards also (we call it
Iteration 1: assume equilibrium in standards). This implies using the new concentration values of
complex in the standards, 𝑥56 , to re-calculate the calibration line. From this new calibration line, we
6
calculate the new concentrations of complex in the samples, 𝑥7 , and, from these, the new constants
𝐾% , 𝐾& and 𝐾(𝑇) for each sample, and a new mean thermodynamic constant 〈𝐾(𝑇)6 〉. You can
6 6 6

check whether the difference between 〈𝐾(𝑇)1 〉 and 〈𝐾(𝑇)6 〉 is significant or not, when compared to
the propagation error of such magnitude (this error will be provided by a program related to the self-
correction of this experience). From here, we could use 〈𝐾(𝑇)6 〉 in the standards and repeat all the
process (new calibration line and new mean equilibrium constant, 〈𝐾(𝑇)0 〉). We call it Iteration 2
(this procedure will be done by the numerical program). You will observe that the difference between
〈𝐾(𝑇)0 〉 and 〈𝐾(𝑇)6 〉 is less significant.
The numerical procedure is an iterative method. This is used when the resolution of a problem
depends on the solution itself. Initially, a value of the unknown magnitude is provided as input and
the solution is calculated (iteration 0) and, with that solution as new input value the unknown
magnitude is re-calculated (iteration 1). After several repetitions, two consecutive solutions are equal
and the final value is obtained, then it is said that the iterative procedure has converged (but it could
not!!).

VARIATION OF THE CALIBRATION LINE:

The calibration line varies significantly from Iterations 0 to 1. To explain how this line varies we
need to observe the variation of two points from the line. There is no variation in absorbances since
these are the measured values. There is only variation in the concentration of complex in each
standard. In Iteration 0, when equilibrium is considered to be fully displaced towards products, the

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

concentration of complex is maximal and equal to the concentration of limiting reactant (𝑥51 = 𝑎). In
Iteration 1, assuming equilibrium in standards, 𝑥56 < 𝑥51 is always fulfilled.
Consider now two points from the line, two standards: standard 1 (with largest absorbance) and
standard 2 (with lowest absorbance). Both standards have been prepared with same amount of KSCN
and Fe(NO3)3, but in standard 2 we have added more HNO3 (see procedure). For standard 1 it stands
6 1 6 1
that 𝑥56 ≤ 𝑥56 and for standard 2 it stands that 𝑥50 ≤ 𝑥50 . We call Δ𝑥56 to the concentration
1 6 1
difference of complex from Iteration 0 to 1: Δ𝑥56 = 𝑥56 − 𝑥56 , same for standard 2: Δ𝑥50 = 𝑥50 −
6
𝑥50 . Both quantities, Δ𝑥56 and Δ𝑥50 , are positive. The calibration line, and thus the slope and y-
intercept, will vary as the relative values Δ𝑥56 and Δ𝑥50 do. That is:
a) If Δ𝑥56 = Δ𝑥50 : the y-intercept increases and the slope remains constant.
b) If Δ𝑥56 > Δ𝑥50 : the y-intercept decreases and the slope increases.
c) If Δ𝑥56 < Δ𝑥50 : the y-intercept increases and the slope decreases
In other words, how the calibration line will vary will depend on which standard (1 or 2) has the
largest error in the initial hypothesis. We will prove that the valid option is c. For this, we need to
know how the ionic strength and, consequently, 𝐾% and 𝐾& for the two standards change, since the
thermodynamic constant K(T) is equal for both. The ionic strength of the standards is determined
basically by the amount of HNO3 and Fe(NO3)3. The concentration of HNO3 is constant for all
standards (solvent), whereas the concentration of Fe(NO3)3 depends on the amount of solvent added
(the more nitric acid added, the lower is the complex concentration because of dilution). Since
standard 2 contains more solvent, the ionic strength of standard 1 will be larger than that of 1: 𝐼56 >
𝐼50 . For this system, a larger ionic strength implies a smaller 𝐾& and, thus, a larger 𝐾% . The following
will stand:
𝐾&,56 < 𝐾&,50 and 𝐾%,56 > 𝐾%,50
The error done in standard p1 is smaller than that in p2 (considering non-equilibrium we can
assume 𝐾% → ∞, so the larger 𝐾% is, the smaller the error done). So this explains that the error in
standard 1 is smaller, Δ𝑥56 < Δ𝑥50 (case c) and, consequently, the y-intercept increases and the slope
decreases in the calibration line when going from Iteration 0 to Iteration 1.

Note that the variation in the calibration line also affects the samples. For a given sample
absorbance, the concentration of complex calculated from the calibration line of Iteration 1 is smaller
6 1
than that obtained with Iteration 0, 𝑥7 < 𝑥7 and, consequently, the calculated 𝐾% diminishes with

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

respect to 𝐾% obtained from Iteration 0, whereas 𝐾& is nearly equal (since the ionic strength of the
samples practically depend on the nitric acid concentration, only). This implies that the calculated
thermodynamic constant is smaller. So, 〈𝐾(𝑇)6 〉 is smaller than 〈𝐾(𝑇)1 〉. Note also that the variation
will be more significant for a smaller sample absorbance. This explains why there is a variation of
the calculated 𝐾% values for the samples in Iteration 0, when in fact there must not be such variation
(the ionic strength is equal for all).

EXPERIMENTATION:
IMPORTANT NOTES:
• It is absolutely forbidden, as usual, to put the spatula inside the reactant containers. In this
experiment it is especially important since the reactants are easily contaminated. Put some
reactant in a watch glass. Never put the remaining reactant back to the container (throw it into
the solid residues container or dilute it and put into the corresponding residues container).
• Work in the fume hood with gloves to prepare all solutions: the samples and the standard
solutions. Do not re-use gloves (throw to the solid residues).
• The colour of solutions containing FeSCN2+ is highly durable. Avoid spilling them (especially
in the colorimeter, the lab workbenches and around the balance, as well as in your personal
objects).

PROCEDURE
All the procedure has to be done with maximum care. The results are highly dependent on this. Weigh
quantities with the weighing funnel, write down the values obtained with the analytical balance. Write
down the molecular mass and the purity of each reactant as shown in the container.
Prepare the following solutions (first ask if any of this is already prepared):
HNO3 0.5 M which we will use as solvent for all solutions (it is prepared)
KSCN 0.002 M (solution A) 250 cm3 (one per 2 groups)
Fe(NO3)3 0.002 M (solution B) 250 cm3 (one per 2 groups)
Fe(NO3)3 0.200 M (solution C) 100 cm3 (one per group)

Make a titration of nitric acid with NaOH, previously standardized with potassium biphtalate. You
can distribute the various titrations among the team members. The team leader has to distribute the
tasks, compile the results and show them to the professor. This parameter, as you will notice while
doing the calculations, is a parameter of foremost importance. So, try to determine the concentration
with the maximum accuracy.
First of all, read carefully the colorimeter manual. The zero read has to be done with HNO3.
Prepare the five samples following the table (quantities in mL). Use the minimum number of
pipettes and write down which will be used for each sample and solution. Measure the absorbances
of each sample (from 1 to 5), from lowest to highest absorbance (from least to most coloured). The
cell has to be cleaned each time. Write down the temperature. Return the sample to the test tube
once it has been measured. Observe and record the colour gradation of the samples.
Next, repeat the procedure with the standard solutions. Do the required measurements so that the
absorbance of all samples are included within the range of the calibration line and stop at that point.
Samples and standards have to be measured in the same lab session (same colorimeter, same zero,

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

same temperature). Return the standard solution to the test tube once it has been measured. Observe
and record the colour gradation of the standard solutions.

MEASUREMENT and ORDER of reactants addition (in the fume hood):

1. Fe(NO₃)₃
2. HNO₃
3. KSCN, mix well and measure as quickly as possible, allowing time for the sample to reach
temperature equilibrium.

Sample Sol. B Sol. A HNO3 Absorbance

M-1 2 2 4
M-2 2 3 3
M-3 2 4 2
M-4 2 5 1
M-5 2 6 0
Standard Sol. C Sol. A HNO3 Absorbance
P-1 5 1 2
P-2 5 1 6
P-3 5 1 10
P-4 5 1 14
P-5 5 1 18
P-6 5 1 22
P-7 5 1 26
P-8 5 1 30
P-9 5 1 34
P-10 5 1 38
…
…
…

In a first stage, we will determine the concentration of complex present at equilibrium comparing
the absorbance of the sample of unknown concentration with that of a standard solution (in the
standards it is supposed, initially, that equilibrium is fully displaced toward the products). Later, and
through a numerical procedure (iterative method) that will be carried out with the supervision of the
professor, the initially approximations made will be adjusted (that is, we will assume equilibrium in
the standards).

RESULTS
1. Do ALL the calculations in a numerical spreadsheet (which will be uploaded to the moodle
space). Include the name of the group in a cell of the sheet.
2. ALL the data used (measurements, molecular masses, volumes, purities, absorbances, etc.) have
to be included in the spreadsheet and only in one cell each. Organize the data plainly and
straightforwardly.
3. When a value is used (measured or calculated) refer to that cell (for example, if the molecular
mass of KSCN is in cell D5, use in the calculation of concentration $D$5). Do NOT copy or
duplicate the values.

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

4. Use the spreadsheet tools to determine the slope and the y-intercept of the lines. Do not copy them
from the graphs.
5. Follow the order of calculations indicated in self-correction. It will guide you and will not allow
you to progress if the calculations are wrong. Check each new value before continuing the
calculations.
Note: the self-correction application works from the error propagation calculation and is
done based on your data. If your experimental data have a large associated error, it is
possible that the application approves an incorrect result (given the width of your error
range). From our experience we know that, eventually, some result will be incorrect and
you will have to search the source of error. In your numerical spreadsheet, leave each cell
with the correct number of significant figures indicated by the calculated error.
6. Consider in each case if the numerical value of a calculation is solid (in order of magnitude).
7. Ask the professor in case of doubt.
8. You have to:
8.1. Calculate the initial concentration of the solutions that you have prepared or titrated. Take
into account the purity of the used reactants.
8.2. Determine the initial concentration (t = 0) of Fe3+ and SCN– for each sample.
8.3. The concentration of complex for each standard solution (assuming fully displaced
equilibrium).
8.4. Determine the calibration line (you will prove the Lambert-Beer law).
8.5. Determine the concentration of complex for each sample from the relationship with the
calibration line.
8.6. Determine the concentration of Fe3+ and SCN– for each sample at equilibrium. Determine
𝐾% .
8.7. Calculate the ionic strength of each sample, the activity coefficient of each species at
equilibrium using Davies law, and determine 𝐾& .
8.8. Determine the equilibrium constant K(T).
8.9. Determine the mean concentration equilibrium constant 𝐾% , and the mean 𝐾& of the five
samples (if they have similar ionic force within your range of error). Determine the mean
equilibrium constant K(T).
8.10. Improve the constant (Iteration 1 and next). Repeat the calculations using the mean
equilibrium constant to determine the concentration of complex in each standard. You need
to determine the ionic strength for each standard. With these concentrations of complex in
the standards you will calculate the calibration line again. And you will repeat steps 8.4 to
8.9. In the spreadsheet there must be the same number of iterations as provided by the self-
correction.
8.11. Discuss the results in the group and with the professor.
8.12. Find out the mean equilibrium constant K(T) and the standard deviation from all the values
obtained by the groups of your team (otherwise indicate the groups). Use the correct values
from Iteration 2 and their propagation errors. Use a value of tp = 2. Use the forum in
the moodle space assigned to your team to communicate. Discuss the results within the team
and with the professor.
8.13. To finish, solve the PRACTICAL CASE that has to be asked for to the professor.

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

POINTS THAT HAVE TO BE KNOWN

1. Working temperature during experimentation.
2. Differences and similarities between sample and standard.
3. Effects of dilution.
4. How to calculate the ionic strength. Effect of the ionic strength upon the concentration
equilibrium constant.
5. Relationship between ionic strength and activity coefficient (see the Davies law for the
calculation of activity coefficients). Ideal systems.
6. Which approximations are done in Iteration 0.
7. The reason that leads us to improve the results.
8. Whether it is a good approximation or not considering a fully displaced equilibrium in the
standards (Iteration 0).
9. How the slope of the calibration line changes.
10. How to explain the variation of the calibration line.
11. Iterative methods.
12. The reason why the professors asked you for a narrow range of error to consider correct the
different values introduced in the self-correction.
13. Understand all the procedure and the explanations. Know how to do the whole the procedure.

REPORT
Include the group’s discussion of the results regarding Kc, Kγ, and K(T), and how they change during
the iterative process. Discuss how the slope and the y-intercept change throughout the iterative
process. Compare the results with bibliography. Compare the ionic strength of the samples and
standards and their changes.
Include a discussion of the value obtained by your team and compare it with bibliography. Determine
the team’s mean value and the corresponding propagation of error and statistical error.
Results and their associated error must be written correctly (see Annex 1).

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

KINETIC STUDY OF REACTION BETWEEN IODIDE AND PERSULFATE

GOAL
To study the kinetics of the reaction between iodide and persulfate (S2O82-) ions in aqueous solution:
S2O82- + 2I- ® 2SO42- + I2 (1)
In the presence of a large excess of iodide ions. Determination of the activation energy of the
reaction.

INTRODUCTION
The rate of the reaction between iodide and persulfate ions can be measured at room temperature. In
this experiment, we will demonstrate that the process is first order for persulfate,
v = kap[S2O82- ] (2)
with measurements of time (tf) at which a given fraction (f) of persulfate has reacted. To determine
this time we use the auxiliary reaction:
2S2O32- + I2 ® S4O62- + 2I- (3)
This reaction is faster than (1), and the I2 produced in reaction (1) disappears right away by reaction
with thiosulfate, S2O32-. If the relative amount of added thiosulfate is smaller than that of persulfate,
thiosulfate will be completely consumed so that iodine that is still being generated in reaction (1)
remains in the solution, appearing the characteristic reddish colour of iodine. Adding starch to the
solution the colouring can be seen more easily, blue in this case. As we know the amount of thiosulfate
added, the quantity of persulfate that has reacted when iodine colouring appears can be calculated.
In reaction kinetics studies it is often used the so-called fractional lifetime, t1/f, which corresponds
to the time of reaction that follows:

𝟏 𝒂=𝒙
𝜏6⁄9 : 𝒇
= 𝒂

where 1/f is the fraction of reactant that remains unreacted at time t1/f. For a first order reaction, it
holds that:

𝒂−𝒙 𝟏
𝒌𝒓 𝝉𝟏⁄𝒇 = −𝒍𝒏 I J = −𝒍𝒏 = 𝒍𝒏𝒇
𝒂 𝒇

The half lifetime t1/2 is the most used and corresponds to the time necessary to reduce the initial
concentration to half:

𝟏 𝒂=𝒂 𝒂@
𝟐
𝜏 6 ⁄0 : 𝟐
= 𝟐
𝒂
= 𝒂
𝒌𝒓 𝝉𝟏⁄𝟐 = 𝒍𝒏𝟐

The lifetime t1/4 corresponds to the time necessary to reduce the initial concentration to one fourth,
that is, that three quarters of the reactant have been consumed:

𝟏 𝒂 = 𝟑𝟒𝒂 𝟏
𝒂
𝜏6⁄A : 𝟒
= 𝒂
= 𝟒𝒂 𝒌𝒓 𝝉𝟏⁄𝟒 = 𝒍𝒏𝟒

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

It can be seen that the fractional time for a first order reaction does not depend on the initial
concentration of reactant. This is an important characteristic, since it allows to make a distinction
between these reactions and those of higher order, which do depend.
Let 𝑭 = x/a be the fraction of reactant that has reacted at a given time. We can write:

𝒂−𝒙 𝒙
𝒌𝒓 𝝉𝟏⁄𝒇 = −𝒍𝒏 I J = −𝒍𝒏 I𝟏 − J = −𝒍𝒏(𝟏 − 𝑭) = 𝒍𝒏𝒇
𝒂 𝒂

and it can be easily proven that:

𝟏 𝟏
𝑭 = 𝟏 − 𝒇 and 𝒇
=𝟏−𝑭

In our case, knowing the initial amounts of thiosulfate and persulfate, the fraction F = x/a that has
reacted can be calculated when the iodine coloration appears. a is the initial concentration of
persulfate in the mixture and x is the concentration of I2 produced in reaction (1) at time t. The time
taken to appear the blue coloration is 𝜏6⁄9 (𝜏6⁄9 is equal to 𝜏6=D ).
So, it can be proved that the reaction is first order with respect to persulfate if the graphical
representation of ln f vs. 𝜏6⁄9 fits to a straight line, and determine the reaction rate constant from the
slope, kap.

ln f = kap · 𝝉𝟏⁄𝒇 (4)

The rate of many reactions increases rapidly with increasing temperature. For simple reactions,
the rate constant follows, with a good approximation, the Arrhenius equation:

𝑬𝒂@
𝒌𝒓 = 𝑨𝒆= 𝑹𝑻

where A and Ea are (practically) constant in a given range of temperature and are the frequency factor
and the activation energy, respectively. This equation can be rewritten as:

𝑬
𝒍𝒏 𝒌𝒓 = 𝒍𝒏𝑨 − 𝑹𝑻𝒂 (5)

Combining expressions (4) and (5) we obtain:

𝑩 𝑬
𝒍𝒏𝝉𝟏/𝒇 = 𝒍𝒏 𝑨 + 𝑹𝑻𝒂 with B = ln f

So, the graphical representation of 𝑙𝑛𝜏6/9 vs. 1/T will provide the activation energy and the
frequency factor.

EXPERIMENTAL PROCEDURE
1) Solution preparation
Prepare the following solutions:
a. 1000 mL of approximately 0.5 M KI solution (already prepared)
b. 250 mL of 0.01 M K2S2O8 solution

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

c. 250 mL of 0.01 M Na2S2O3 solution

2) Determination of activation energy

In this experience temperature is varied while 1/f factor is maintained constant in order to
calculate activation energy. First experiment is performed at room temperature (outside of the
thermostatic bath) and it is repeated at the following temperatures: 25oC, 30oC, 35oC, 40oC,
45oC, 50oC. Take note of the temperature of the reaction mixture (not the thermostatic bath).

10 ml of KI 0.5 M solution are introduced into an Erlenmeyer. In a second Erlenmeyer, 10 ml

of persulfate 0.01 M solution, a few drops of starch solution and 10 ml of thiosulfate 0.01 M
solution are mixed. Both Erlenmeyer are introduced inside of the thermostatic bath with
stirring.

Once thermal equilibrium is achieved, the content of the two Erlenmeyer flasks is mixed as
fast as possible. Time is measured, with as much precision as possible, until a yellowish colour
appears in the solution. Initial time must be registered when approximately half of one
solution has been added to the other.

Tasks:
a. Calculate 1/f factor for each experiment and explain what this means.
b. Calculate the excess of iodide.
c. Plot ln t1/f against 1/T (K-1) and determine the frequency factor (s-1) and the activation
energy (kcal·mol-1).
d. Calculate, approximately, the rate constant at each of the used temperatures.
e. Plot ln kr against 1/T (K-1) and determine the frequency factor (s-1) and the activation
energy (kcal·mol-1). Compare with the results obtained in part (c). Which plot could
be more useful? Justify your answer.
f. Problem: 20 ml of KI 0.5 M solution are introduced in the first Erlenmeyer. In the
second one, 20 ml of persulfate 0.01 M solution are introduced as well as, in successive
experiments, 20 ml, 10 ml and 5 ml of thiosulfate 0.01 M solution. Calculate the excess
of iodide and 1/f factor for each of these three experiments.
g. Discuss your results.

3) OPTIONAL: Determination of the rate constant

In this second experience the procedure is similar to the one described in the previous section.
The objective now is to determine the first order rate constant with respect to persulfate at
25oC. 20 ml of KI 0.5 M solution are introduced into an Erlenmeyer. In a second Erlenmeyer,
20 ml of persulfate 0.01 M solution, a few drops of starch solution and 20 ml of thiosulfate
0.01 M solution are mixed. Both Erlenmeyer are introduced inside of the thermostatic bath.

Repeat the same experiment two more times, using this time 10 ml and 5 ml respectively of
thiosulfate 0.01 M instead of 20 ml.

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

Set the thermostat at 25 oC for these experiments and mix the contents of the two Erlenmeyer
flasks once thermal equilibrium is achieved. Write down the time as accurately as possible.
Stir continuously throughout the experiment.

Tasks:
a. Make a plot of ln f vs. 𝜏6⁄9 (in seconds) and check that the reaction is first order with
respect to persulfate. Fit the data to a straight line equation to determine the rate
constant at 25oC from the slope.
b. Discuss your results.

REMEMBER: Perform all the calculations in a single spreadsheet. This spreadsheet must be
delivered in the Moodle space with the required name. Include clearly the name of the group in a cell
of the spreadsheet. Remember that a report is also expected, this should include a brief introduction
to the practice (not more than a page), obtained results with labeled graphics and conclusions. This
report should also include all the tasks mentioned above. Do not forget to adequately cite any
bibliographical reference that you might use for such report.

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

DETERMINATION BY CONDUCTIMETRY OF THE RATE OF

SAPONIFICATION OF ETHYL ACETATE

GOAL
Apply the conductimetric method to determine the total order and the reaction rate constant of the
saponification reaction of ethyl acetate in basic medium.
Learn to determine the propagation error of some magnitude and the standard deviation of the
mean value.

INTRODUCTION
Saponification of ethyl acetate is relatively fast at 25oC following the process:

CH3COOC2H5 + Na+OH– → CH3COO–Na+ + C2H5OH

During the reaction, the OH– ions are replaced by acetate. The conductivity of the OH– ion is
greater than that of acetate ion. The ethyl acetate and the alcohol formed are not ionic and they do not
affect the conductivity measurements, in practice. So, the chemical reaction can be monitored by
conductimetry since this magnitude decreases along the reaction.
If the reaction is irreversible and, thus, the products do not affect the reaction rate, the rate equation
can be written as:

K[M]
KO
= 𝑘P [CHQ COOC0 HR ]P [NaOH]S (1)

Or

K[M]
KO
= 𝑘P (𝑎 − 𝑥)P (𝑏 − 𝑥)S (2)

where
• a is the initial concentration of ethyl acetate
• b is the initial concentration of sodium hydroxide
• x is the concentration of reactant that reacts at time t
If we work with equal initial concentrations of reactants (a = b), equation (2) transforms into:

K[M]
KO
= 𝑘P (𝑎 − 𝑥)PTS = 𝑘P (𝑎 − 𝑥)U (3)

where n is the total order of reaction.

The integrated first and second order reaction equations are:

V=W
𝑛=1 𝑙𝑛 I J = −𝑘P 𝑡 (4)
V

6 6
𝑛=2 V=W
− V = 𝑘P 𝑡 (5)

Also, labelling:

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

• k0 the initial specific conductivity of the solution

• kt the specific conductivity of the solution at time t
• kf the final specific conductivity of the solution
we can express x as a function of the specific conductivities:

X =X
𝑥 = 𝑎 X &=X * (6)
& +

Substituting equation (6) into equations (4) and (5) we obtain the integrated rate equations for this
reaction in terms of conductivity:

X* =X+
𝑛=1 𝑙𝑛 X = −𝑘P 𝑡 (7)
& =X+

X& =X*
𝑛=2 X* =X+
= 𝑎 · 𝑘P 𝑡 (8)

So, from the integrated equations for first and second order as function of the conductivities and
the initial concentration of both reactants, we can determine the total reaction order and the rate
constant for the studied process.

EXPERIMENTAL PROCEDURE
1. For the experimental procedure, potassium biphtalate and KCl are needed, and they must be
in the oven in advance. Do not weigh hot substances.
2. Write down the characteristics of the material used: the maximum volume of the glass
material, if it is class A or B, the number of filled-to-the-mark volumes, etc. This is all
important for the determination of propagation error.
3. Put the thermostatic bath at 25oC.
4. Prepare 1000 mL of 0.1 M NaOH solution. Ask in advance if
there is some of it prepared. This solution is shared among all
groups.
5. Titrate the 0.1 M NaOH solution (standardization) with
potassium biphtalate and determine the concentration of the
solution. This task can be shared between all the members of the
team. Do a minimum of 2 titrations per group. You will use an
automatic titration apparatus. Ask the professor. Write down
the volume of NaOH added and the weight of potassium
biphtalate of each titration. Determine the concentration of the
solution. Collect the data of all the team and hand it out to the
professor. Correct this value with the professor before continuing the procedure. The
professor will provide you with the necessary data to do steps 4 and 5.
6. Prepare 100 mL of ethyl acetate 0.1 M solution (Solution 1), of concentration as similar as
possible to that of the titrated NaOH one. Ask the professor before weighing. Recall that the
experiment has been based on identical initial concentrations of ethyl acetate and sodium
hydroxide. This solution is shared among all groups. Prepare the solution just before use.

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

7. Prepare 100 mL of sodium acetate 0.1 M (Solution 2), of concentration as similar as possible
to that of the titrated NaOH one. Ask the professor before weighing. This solution is shared
among all groups.
8. Prepare by dilution (use non-graduated pipettes) the following solutions:
• Dilution 1: 100 mL of NaOH 0.01 M.
• Dilution 2: 50 mL of NaOH 0.02 M.
• Dilution 3: 50 mL of ethyl acetate 0.02 M. Prepare just before use.
• Dilution 4: 100 mL of sodium acetate 0.01 M
9. Prepare 1000 mL of KCl 0.01 M solution (KCl solution). This is shared among all groups.
10. Put Dilution 1, Dilution 2 and Dilution 3 into the thermostatic bath until thermal equilibrium
is reached (approx. 15 minutes).
11. Calibrate the conductimeter with KCl solution. Write down the cell constant. Before this,
read the manual of the apparatus assigned. Set to zero the temperature coefficient. Stir the
solution while measuring.
12. Measurement of k0. Wash the conductivity cell several times with deionized water and finally
with the problem solution. Measure the conductivity of the NaOH 0.01 M solution (Dilution
1). Stir the solution while measuring. Do the measurement several times until the conductivity
does not change. All the measurements must be done at 25oC. At the end, wash several times
the conductivity cell with deionized water again.
13. Put Dilution 4 into the thermostatic bath until thermal equilibrium (approx. 15 minutes).
14. Measurement of kt. Put the thermostatized solution of NaOH 0.02 M (Dilution 2) into that of
ethyl acetate 0.02 M (Dilution 3). Stir it vigorously and simultaneously start the chronometer.
Cover the beaker, leaving inside the cell, the temperature sensor and the magnet. Measure the
conductivity as soon as possible (note the time of this first measurement). Without removing
the conductivity cell, measure the specific conductivity at the following time intervals:
a. 3 more measurements every ½ minute.
b. 6 measurements every minute.
c. 20 measurements every 3 minutes (1 hour in total), or until the conductivity is
practically constant.
15. Measurement of kf. Wash the conductivity cell several times with deionized water and finally
with the problem solution. Measure the conductivity of the sodium acetate 0.01 M solution
(Dilution 4). Stir the solution while measuring. Do the measurement several times until the
conductivity does not change.

ORGANIZATION OF DATA AND RESULTS

1. Use one numerical spreadsheet only for all the calculations of this experience. ALL
measurements, molecular masses, purities, type of material and the errors associated to
measurement apparatus, have to be clearly visible in one cell each, to which all the
calculations will refer to. Organize the data plainly and straightforwardly.
2. Introduce all the data in the self-correction application. Check each result by the self-
correction procedure.
3. In the spreadsheet, calculate the concentration of the NaOH 0.1 M solution (standardization)
and its error (see Annex 1). Calculate the standard deviation of the average and the
propagation error.

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

4. In the spreadsheet, calculate the real concentration of Solution 1 and its error.
5. In the spreadsheet, calculate the real concentration of Solution 2 and its error.
6. In the spreadsheet, calculate the real concentration of Dilutions 1, 2, 3 and 4 and their errors.
7. Make a table with time (in seconds) and specific conductivity measurements. Also include
the values of k0 and kf.
8. Calculate the values corresponding to the rate equation expressions of first and second order
(use the concentration provided by self-correction).
9. Represent the first and second order rate equations as a function of time. Find the y-intercept
and the slope of the lines with the functions provided by the spreadsheet.
10. Obtain the total reaction order and the rate constant.
11. Express the results with appropriate units and significant figures.
12. Discuss the results.
13. Upload the spreadsheet to the Moodle space of the course with the corresponding name.

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

ANNEX I:
RESULTS AND ERRORS
1. Error associated to a magnitude (x) resulting from n independent experimental measurements (xi).
1.1. Calculate the sampling average (mean value):
U
1
𝑥̅ = 3 𝑥/
𝑛
/Y6

1.2. Calculate the sampling standard deviation:

∑U (𝑥/ − 𝑥̅ )0
𝜎U=6 = p /Y6
𝑛−1
1.3. Calculate the interval boundaries:
𝑥̅ ± 𝑡5 𝜎U=6
where 𝑡5 (the Student parameter) is an adimensional value associated to a given confidence
range and a given number of measurements (n). Ask the professor for data.
1.4. Determine if all the values are comprised within the interval defined by the average and its
boundaries. If any value, xi, fall off the interval, it must be eliminated and the average, the
sampling standard deviation and the boundaries re-calculated with the new set of values. Do
all the procedure as many times as necessary until all values fall within the boundaries.
1.5. If all the values, xi, are within this interval, express the magnitude as the average and its
confidence interval:
𝜎U=6
𝑥̅ ± 𝑡5
√𝑛
Z,$-
where is the standard deviation of the average.
√U

2. Another type of error is the propagation error. It is the only one that can be calculated when a
single measurement is done (for example, a solution preparation). It is the error associated to the
material used in the laboratory (balance, pipet, etc.) and to the mathematical expression applied
to determine the corresponding magnitude. You have to ask the professor for the errors associated
to the material used.
2.1. Determination of the propagation error.
Let x be a magnitude not directly measured, which can be obtained from two experimental
data a and b. So, x is a function of a and b:
x = f (a,b)
The error of the magnitude x, 𝑑𝑥 , is associated to the error (or uncertainty) in the
measurement of a and b (𝑑𝑎 and 𝑑𝑏 , respectively). This error is calculated using the
expression:

𝜕𝑥 0 𝜕𝑥 0
𝑑𝑥 = pt v (𝑑𝑎) + t v (𝑑𝑏)0
0
𝜕𝑎 𝜕𝑏
2.2. The magnitude can be expressed as 𝑥 ± 𝑑𝑥.
3. If a magnitude is determined from an average, the average standard deviation and the propagation
error can be calculated. We will use the largest of both to express the final average magnitude.

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 Physical Chemistry Laboratory. Equilibrium and kinetics block

4. How to numerically express a result: criteria.

4.1. The error is expressed only with a significant figure. The magnitude is expressed according
to the error.
Example 1: 12684.415463434 ± 4.26579874 12684. ± 4.
Example 2: 12684.415463434 ± 42.6579874 12680. ± 40. (1268. ± 4.)·101
Example 3: 12684.415463434 ± 0.426579874 12684.4 ± 0.4 (126844. ± 4.)·10-1
4.2. Considering the next figures:
Example 1: 12685.8794 ± 4.78579874 12686. ± 5.
Example 2: 12685.8794 ± 47.8579874 12690. ± 50. (1269. ± 5.)·101
Example 3: 12685.8794 ± 0.478579874 12685.9 ± 0.5 (126859. ± 5.)·10-1
4.3. Special case:
If the significant figure of the error is 1 or 2, the error is expressed with two significant
figures, as long as the value of both figures is SMALLER THAN 25 (that is, when the first
three figures of the error are between 100 and 249):
Example 1: 12685.8194 ± 1.71579874 12685.8 ± 1.7
Example 2: 12685.8794 ± 1.77579874 12685.9 ± 1.8
Example 3: 12685.8194 ± 2.71579874 12686. ± 3.
Example 4: 12685.8194 ± 2.48579874 12685.8 ± 2.5
Example 5: 12685.8194 ± 2.50579874 12686. ± 3.
Note that:
Example 6: 126851.104 ± 10.119874 126851. ± 10.
Example 7: 126851.104 ± 30.119874 126850. ± 30.

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