Kinetics Lab Manual
Kinetics Lab Manual
Faculty of Sciences
Section V
Nabatieh
1 Dr Bachar KOUBAISSY
Experiment 1
Kinetics of a pseudo-first order reaction
Oxidation of the iodide ion by the persulfate ion
I. Objective
a) To show that the reaction between iodide ion (I- ) and persulfate ion (S2O82-) is of first
order with respect to the persulfate ion.
b) To determine the reaction rate constant at a given temperature and the half-life time
t1/2.
c) To observe the influence of Cu2+ on the reaction rate.
II. Theory
The persulfate ion S2O82- is a powerful oxidant. It has a great tendency to gain two electrons
and yield the SO42-:
S2O82- + 2 e- → 2 SO42-
Iodide ion can be easily oxidized by S2O82-
2 I- → 2 e- + I2
The purpose of this experiment is to determine the rate law for the reaction between persulfate
ion, S2O82-, and iodide ion, I-:
The rate of this reaction can be monitored with a spectrophotometer because the product I2
reacts with excess I- in the solution to form the colored species I3-, triiodide Which is soluble
in aqueous solution. The absorbance due to triiodide increases during the course of the
reaction as it is being produced and can be used as a measure of the rate versus time.
I2 + I- →I3- (2)
Rate of disappearance of S2O82- = rate of appearance of I2 = rate of appearance of I3- =
k[S2O 2-]x[I-]y
8
It has been demonstrated that this reaction is of first order with respect to each of S2O82- and I-
ions .
The rate law can be written as:
d S2O82−
Reaction rate = r = − = K[S2O82-][I-]
dt
Where the iodide is used in large excess, the iodide concentration will vary little , and we can
consider as constant, so we can write Reaction rate =r= K[S2O82-][I-] =Ḱ [S2O82-] (3) where
Ḱ= K[I-] (in this case the reaction is called a pseudo first order.
Supposing that a is the initial concentration of persulfate, b the initial concentration of iodide,
x the number of moles of S2O 2- per unit of volume that have reacted at time t, so we can write
8
dx
at any time t, [S2O82-] = (a-x) r= = Ḱ (a-x).
dt
2 Dr Bachar KOUBAISSY
The equation integration between t = 0 and t gives:
Ln(a-x) = Ln(a) - Ḱ t.
In order to determine Ḱ , we have to determine x at different time, for that we measure the
absorbance at different time:
At the time t : At = λx
At the end of the reaction A∞ = λa
A a A a
Then A∞ - At = λ(a-x) and = and finally Ln = Ln = Ḱ t
A − At a − x A − At a−x
A
Plot the function Ln versus time (slope Ḱ = K.b)
A - A t
III. Materials and chemicals
-Erlenmeyer flasks of 100mL
-Beakers
-Volumetric pipettes 25mL and 10mL
- Agitator, magnetic stirrer
- Chronometer
-Volumetric flask of 100 mL
-Spectrophotometer
- K2S2O8 solution of concentration 0.05mol/L
-KI solution of concentration
-Cu(NO3)2
IV. Procedure
Part 1:
a- Fill 7 Erlenmeyer flasks, each one with 100mL distilled water (by using a volumetric
flask.
b- Add 100mL of the KI to the beaker.
c- Place the beaker on the agitator.
d- Add 25mL of K2S2O8 solution to the beaker by using a 25 mL volumetric pipet.
e- Start the chronometer when half of the quantity of K2S2O8 is added and let it run till
the end of the experiment.
f- Transfer 10 mL of the mixture solution to the water in the Erlenmeyer flask number 1,
note the time t1 (when half of the quantity is added) and then add the same quantity
every 3 minutes to have 7 samples.
g- Put a sample of the obtained solution present in each Erlenmeyer in the
spectrophotometer tube (cuvet). Measure the absorbance of the solution using the
spectrophotometer at λ= 435nm.
h- Keep the initial beaker containing the remaining solution, add about 0.5 mL of Cu2+
solution in order to measure absorbance at the end of the experiment.
3 Dr Bachar KOUBAISSY
Part 2:
Repeat the experiment in part 1, but upon adding 0.5mL of Cu2+ to the 25 mL of K2S2O8
solution, before making the reaction mixture, and then proceeding as described in part 1.
4 Dr Bachar KOUBAISSY
Experiment 1
Kinetics of a pseudo-first order reaction
Oxidation of the iodide ion by the persulfate ion
Group Date
Slope = K1 = t1/2 =
Slope = K2 = t1/2 =
5 Dr Bachar KOUBAISSY
Experiment 2
Saponification of Ethyl acetate
Kinetic study of a second-order reaction
By conductimetry.
I. Objective
To determine using conductance measurements:
- The order of the reaction
- The rate constant K
- The half period t1/2
- The activation energy
II. Theory
In the bimolecular reaction, the saponification of ethyl acetate
CH3COOC2H5 + NaOH → CH3COONa +C2H5OH
The progress of the reaction may be followed by titrating the quantities of NaOH present from
time to time with standard acid; or it may be followed by observing the change in electrical
conductance as sodium hydroxide consumed and sodium acetate formed or by following the
variation of the pH versus time.
It is convenient to use initial concentrations of the reacting substances. This permits one the
simplified second order equation for calculating the rate constant in which a = b.
Electrolytes are substances which dissolve in water to produce a solution which conducts an
electrical current. Such substances produce ions when dissolved in water, and it is the ions
which carry the current through the solution. Electrolytes are classified as either strong
electrolytes or weak electrolytes. Strong electrolytes when dissolved in water react
completely to produce ions.
Electrolytes obey Ohm’s law. The Resistance (R) is defined:
.L
R= = K. (K = L/S)
S
: Specific resistivity
L: length of the solution (conductimeter cell)
S: cross section of the column
6 Dr Bachar KOUBAISSY
cubic centimetre of solvent in a chemical composition. Equivalent conductivity is the inverse
1 1 S
of resistance = = = . =K.
R .L / S L
On other hand equivalent conductivity depends on the electrolyte nature and its concentration
and the temperature. So specific conductivity is related to concentration by: = .C
The specific conductance of the reaction mixture is determined by the presence of
the free mobile ions. involves the respective molar conductivities of the ions (λi) and the
corresponding molar ion concentrations (Ci): = i.Ci
Conductivity probe measure the conductivity of the solution. In the present experiment,
hydroxide ion and acetate ion would contribute to the conductivity of the solution. Let 0 be
conductivity of the solution at the start of the reaction. At the begening of the reaction, only
sodium hydroxide would contribute to the conductivity. As reaction proceeds, sodium acetate
starts forming after consumption of sodium hydroxide resulting in different conductivity
results. The consumption of NaOH can be found using the following relationship:
0 − a
=
t − a − x
7 Dr Bachar KOUBAISSY
III. Materials and Chemicals:
- Beakers 50mL and 150 mL
- Volumetric pipet 25mL
- Agitator, magnetic stirrer, glass bar
- Water bath
- Chronometer
- Conductimeter
- NaOH solution (0.02 mol/L)
- Ethyl acetate (0.02 mol/L)
IV. Procedure
Part 1 :
a- Take 50 mL of NaOH solution (0.02 mol/L) and introduce it in a 150 mL beaker
b- Take 50 mL of ethyl acetate (0.02 mol/L) and introduce it in a 50 mL beaker
c- Mix the two solutions in a 150 mL beaker. Start the chronometer when half of the
quantity of ethyl acetate is added and let it run till the end of the experiment
d- Quickly take the first value of the conductivity by putting the conductimeter cell into
the solution
e- Measure the conductivity of the solution every 3 minutes
f- Keep the mixture until the end of the experiment in order to measure χ∞
Part 2 :
a- Prepare the water bath and regulate the temperature T2 = T1 + 10°C.
b- Put each solution of NaOH and ethyl acetate in 2 separate beakers and immerse
thermometers in the solutions until the temperature becomes T1+10°C, then mix the two
solutions.
c- Continue the same steps as in part one
d- Take values every 2 minutes.
8 Dr Bachar KOUBAISSY
Experiment 2
Kinetics of a second-order reaction
Saponification of Ethyl acetate
Group Date :
1
Slope = = K1 = t1/2 =
0 −
T2 =
1
Slope = = K2 = t1/2 =
0 −
9 Dr Bachar KOUBAISSY
Experiment 3
Kinetics of a pseudo first order reaction
Oxidation of I- by S2O82-
I. Objective:
1- Realisation of experimental conditions to obtain a degeneration of order.
2- Determine the order of the reaction w. r. t of each reactant
3- Verify a kinetic law: concentration= f(time)
4- Determine the rate constant k and half time reaction t1/2.
II. Theory:
The purpose of this experiment is to determine the rate law for the reaction between persulfate
ion, S2O82-, and iodide ion, I-:
It has been demonstrated that this reaction is of first order with respect to each of S2O82- and I-
ions. The rate law can be written as:
d S2O82−
Reaction rate = r = = K[S2O 2-][I-]
8
dt
If the concentration of I- is maintained constant, the rate expression becomes:
r = Ḱ [S2O 2-]
8
Where Ḱ = K[I-] (in this case the reaction is called of a pseudo first order).
The determination of the rate could be done by finding the necessary time to form n moles of
I2. This can be carried out in the presence of thiosulfate ion, S2O32-.
The reaction that occurs is:
I2(aq) + 2 S2O32-(aq) → 2 I- + S4O62-(aq) (2)
This reaction is fast and gives I-, for that [I-] is maintained constant during this experiment
At any time [S2O 2-] = (a-x)
8
dx
r= = Ḱ (a-x).
dt
The equation integration between t=0 and t gives:
a
Ln(a-x) = Ln a - Ḱ t. plot Ln versus time (slope = Ḱ = K.[I-]).
a−x
10 Dr Bachar KOUBAISSY
III. Materials and Chemicals:
- 100mL volumetric flask
- 600mL beaker
- Burette
-Agitator
-Chronometer
- KI solution (0.16mol/L)
-K2S2O8 (0.08 mol/L)
-Na2S2O3 (0.25 mol/L)
IV. Procedure:
a- Fill the burette with Na2S2O3 solution.
b- Take 200 mL distilled water and introduce it in a 600 mL beaker.
c- Add 100 mL KI to the above 600 mL beaker .
d- Add 1mL S2O32- from the burette on the solution in the beaker.
e- Put the beaker on the magnetic stirrer.
f- Add 100 mL K2S2O8 solution to the solution in the beaker. Start the chronometer when
half of the quantity of K2S2O8 is added, and let it run till the end of the experiment
g- Note the time t1 necessary for the appearance of yellow color due to I2 and add again
1mL of the solution of S2O32- (the yellow color will disappear). Note the time t2
necessary for the reappearance of the yellow color, then add agin another mL of the
solution of S2O32-....
h- Repeat adding 1 mL of S2O32- 8 times.
11 Dr Bachar KOUBAISSY
Experiment 3
Kinetics of a pseudo first order reaction
Oxidation of I- by S2O82-
Group Date
Slope = K= t1/2 =
12 Dr Bachar KOUBAISSY
Experiment 4
Study of the kinetic of the hydrolysis reaction
of ethyl acetate by titration.
I. Objective:
1. Determine the order of the reaction.
2. Determine the rate constant.
3. Determine the half-life period.
II. Theory
The hydrolysis reaction of ethyl acetate by hydroxide is as following:
CH3COOC2H5 + NaOH → CH3COONa +C2H5OH
To determine the partial orders of the reaction with respect to ester and hydroxide ion, we
have to study the type of reactions
dx
r= = K[CH3COOC2H5]α[HO-]β
dt
During the reaction, the mixture of ethyl acetate and sodium hydroxide is taken by pipette at
different time and mixed with excess of HCl.
The progress of the reaction may be followed by titrating the quantity of HCl remaining at
different time by NaOH.
NaOH concentration change with progress of the reaction.
In order to determine the order, we have to plot 3 graphs :
dx
1- If the reaction of order 0 we obtain r = = K Ct = C0 - Kt
dt
2- For the reaction of order 1 with respect to HO - and 0 with respect to ester, we obtain
d HO − C
r=− = K.[HO-] Ln 0 = Kt
dt Ct
3- For the reaction of order 1 with respect to HO - and 1 with respect to ester, we obtain
d HO −
r=− = K[HO-][ CH3COOC2H5] if [HO-] = [ CH3COOC2H5] we obtain:
dt
1 1
− = Kt
Ct C0
We deduce the order of the reaction when we obtain straight line.
13 Dr Bachar KOUBAISSY
III. Materials and chemicals
- Burette
- 6 Erlenmeyer flasks
- Beaker
- Volumetric pipette 10mL
- Magnetic stirrer
- Volumetric flask 100mL
- Chronometer
- NaOH solution (0.1mol/L)
- HCl solution (0.1mol/L)
- Ethyl acetate solution (0.1mol/L)
- Phenolphthalein
IV. Procedure
a. Fill the burette with NaOH
b. Fill 6 Erlenmeyer flasks with 10mL HCl
c. Add 100mL ethyl acetate in a beaker and put it on the magnetic stirrer
d. Take 100mL NaOH, add it to the beaker containing ethyl acetate. Start chronometer
when half of the quantity of NaOH is added and let it run till the end of the experiment
e. At a definite interval of time, take 10mL of the mixture and introduce them in the first
Erlenmeyer flask.
f. Add few drops of phenolphthalein to the first Erlenmeyer flask and titrate it with
NaOH from the burette, until a pink color appears which indicate Veq
g. Repeat the same procedure for the 5 other Erlenmeyer flasks and record the
equivalence volume of NaOH obtained for each sample.
14 Dr Bachar KOUBAISSY
Experiment 4
Study of the kinetic of the hydrolysis reaction
of ethyl acetate by dosage
Group Date
Time(min)
Veq NaOH(mL)
[OH-]t mol/L
Ct
Ln(C0/Ct)
1/Ct
Slope = K= t1/2 =
15 Dr Bachar KOUBAISSY
Experiment 5
Determination of rates (initial) and activation
energy of the oxidation reaction of iodide
ion by persulfate ion
I. Objective:
1- Determine the initial rate of the oxidation reaction of iodide ion by persulfate ion at
different temperatures
2- To deduce the activation energy of the reaction
II. Theory
(See experiment 3)
The temperature dependence of the rate constant is given by:
E
−
K = Ae RT
(1)
Equation (1) is called the Arrhenius Equation, where A is the pre-exponential factor, E is the
activation energy with units of J/mol, T is the absolute temperature, and R is the gas constant
(R= 8.3145 J K-1 mol-1). Equation (1) can also be written in the form :
E
LnK = LnA − (2)
RT
According to equation (2) the activation energy can be obtained by measuring the rate
constant at several temperatures, and then plotting Ln k versus 1/T.
16 Dr Bachar KOUBAISSY
IV. Procedure:
Part 1:
a- Fill the burette by Na2S2O3
b- Fill 4 Erlenmeyers each one by 100 mL distilled water
c- Take 25 mL KI and put them in a beaker
d- Take 25mL K2S2O8 solution, and introduce them in the beaker containing KI. Start
chronometer when half of the quantity of K2S2O8 is added and let it run till the end of
the experiment
e- After 2minutes, take 10mL of the solution and put it in Erlenmeyer number 1, and note
the time t1.
f- Repeat the same procedure for the other Erlenmeyers every 2 minutes. Record t2, t3, t4.
g- Add few drops of starch in every erlenmeyer. Titrate the 4 solutions with thiosulfate.
Note Veq obtained after each titration.
Part 2:
a- Prepare the water bath and regulate the temperature T2 = T1 + 10°C.
b- Put each solution of KI and K2S2O8 in 2 separate beakers and immerse thermometers in the.
solutions until the temperature becomes T1 + 10°C, then mix the two solutions.
c- Continue the same steps as in part one.
17 Dr Bachar KOUBAISSY
Experiment 5
Determination of initial rates and activation
energy of the oxidation reaction of iodide
ion by persulfate ion.
Group Date
T1 =
Time (min) Volume of Na2S2O3 (mL) [I2] mol/L
Rate1 =
T2 =
Time(min) Volume of Na2S2O3 (mL) [I2] mol/L
Rate2 =
18 Dr Bachar KOUBAISSY
Experiment 6
Determination of disappearance rate of hydroxide ions
I. Objective
1. Show that the saponification reaction of ethyl acetate is of first order relative to hydroxide
ions.
2. Determine rate constant of reaction and half-life period
II. Theory
The saponification of ethyl acetate is slow at room temperature
CH3COOC2H5 + NaOH → CH3COONa + C2H5OH
The progress of the reaction may be followed by measuring the pH of the mixture at different
time. It has been demonstrated that this reaction is of first order with respect to each of
CH3COOC2H5 and HO-. The rate law can be written as:
dx
Reaction rate = r = = K[CH3COOC2H5][HO-] = K (a-x)(b-x)
dt
CH3COOC2H5 is in great excess, so it approximately remains constant and doesn’t affect the
rate of reaction, so we can write:
dx
r= = K(a-x)b = Ḱ (a-x)
dt
10−14 10−14
Ln(a-x)=Ln(a)-K’t where a= HO − = a-x = HO − =
0 H + t H +
0 t
K'
Finally pHt = pH0 - t
2.3
We can plot pH obtained versus time in order to determine the real rate constant of the
reaction.
19 Dr Bachar KOUBAISSY
IV. Procedure
a- Take 49 mL of distilled water and put it in a beaker.
b- Add 50 mL NaOH to the beaker containing distilled water.
c- Put the beaker on the magnetic stirrer, introduce the pH electrode and record pH0
d- Add 1mL pure ethyl acetate. Start chronometer when half of the quantity of ethyl
acetate is added and let it run till the end of the experiment
e- Record the different pH at different times (∆t = 30 s)
20 Dr Bachar KOUBAISSY
Experiment 6
Determination of disappearance rate of hydroxide ions
Group Date
Slope = K= t1/2 =
21 Dr Bachar KOUBAISSY
Experiment 7
Kinetics of sucrose inversion by polarimeter
Objective:
d) To show that the inversion reaction of sucrose is of first order with respect to the
sucrose.
e) To determine the reaction rate constant.
Principle
The inversion reaction of sucrose, which is catalysed by protons, produces invert sugar, which
is a mixture of glucose and fructose. The reaction is accompanied by a change in the optical
rotation of the system. Glucose rotates the polarisation plane of linearly polarised light to the
right, while inverted sugar rotates it to the left.
A half-shade polarimeter is used for the measurement of the change in the angle of rotation of
polarised light during the inversion reaction of sucrose over time.
Optical activity is the ability of certain substances to rotate the plane of vibration of linearly
polarised light. When linearly polarised light passes through such a substance, the radiation
components are shifted in phase due to the interaction of substances which contain
asymmetric carbon atoms. This phase shift is seen as a rotation of the plane of polarisation.
A change of the concentration corresponds to a change of the angle of rotation because
concentration is proportional to rotation angle :
α= αs. l. C
α : angle of rotation, αs : specific angle of rotation, C : concentration, l: path length in the
solution.
In an acidic environment, sucrose undergoes hydrolytic cleavage into glucose and fructose, in
a process catalysed by oxonium ions. Dextrorotatory sucrose is converted into dextrorotatory
glucose and laevorotatory fructose.
22 Dr Bachar KOUBAISSY
It has been demonstrated that this reaction is of first order with respect to each of sucrose and
H2O.
dx
r= = K[C12H22O11][H2O]= K (a-x)(b-x)
dt
Overall, this reaction corresponds to a pseudo-first order reaction, i.e. the reaction rate
depends only on the sucrose concentration.
dx
r= =K(a-x)b=K’(a-x)
dt
The equation integration between t = 0 and t gives: Ln(a-x) = Ln(a) - Ḱ t.
In order to determine Ḱ, we have to determine x at different time, for that we measure the
rotation angles at different time.
At t=0 α0 = λa
At the time t αt=αS+α G+ αF= λ (a-x) + λ’(x)+ λ’’(x)
At the end of the reaction α∞=λ’(a) + λ’’(a)
Then αt- α∞= (λ -λ’- λ’’) (a-x)
α0- α∞ = (λ -λ’- λ’’) a
So = and finally Ln = Ln = Ḱ t
IV. Procedure
A. Determination of α0
1- Take 25 mL of sucrose solution and introduce it in a 50 mL volumetric flask. Add
water till the mark of volumetric flask
2- Put a sample in the polarimeter tube and measure the rotation angle of solution.
B. Determination of α∞
1- Take 25 mL of sucrose solution and introduce it in a 50 mL volumetric flask. Add
24ml of water then fill with concentrated HCl till the mark of volumetric flask.
23 Dr Bachar KOUBAISSY
2- Put the solution in a boiling water bath for 10minuters. Then cool the solution to the
initial temperature. Complete with water to the mark if necessary.
3- Put a sample in the polarimeter tube and measure the rotation angle of solution.
C. Study of the variation of the angle rotation at different time in HCl 1.5 M
medium
1. Take 25 mL of sucrose solution and introduce it in a 50 mL volumetric flask. Add 10
ml of water then fill with HCl 5M till the mark of volumetric flask. Start the
chronometer when you add the HCl. Measure the rotation angle at different t, take 7
values with ∆t= 3min.
D. Study of the variation of the angle rotation at different time in HCl 2 M medium
2. Take 25 mL of sucrose solution and introduce it in a 50 mL volumetric flask. Add 5
ml of water then fill with HCl 5M till the mark of volumetric flask. Start the
chronometer when you add the HCl. Measure the rotation angle at different t, take 7
values with ∆t= 3min.
24 Dr Bachar KOUBAISSY
Experiment 7
Kinetics of sucrose inversion
Group Date
[H2O]= α0 = α∞=
Time (min) Ln
Slope = K1 = t1/2=
Time (min) Ln
Slope = K2 = t1/2=
25 Dr Bachar KOUBAISSY