Kinetics Lab

Experiment 2 – Inversion of sucrose

Purpose: The rate of reaction between sucrose and water catalyzed by the Hydrochloric acid (H +
ions) is followed by measuring the angle of rotation of polarized light passing through the
solution. The angle of rotation of polarized light passing through the solution is measured with a
polarimeter.

Condition: Working with chiral molecules that can rotate the light.

Introduction
𝐇+
The reaction is C12H22O11 + H2O → C6H12O6 + C6H12O6
Sucrose Glucose Fructose
Sucrose, glucose and fructose are 3 chiral molecules that can
rotate the light. Glucose and fructose are considered as
enantiomers (mirror images of each other).

Sucrose is dextrorotatory, but the resulting mixture of glucose

and fructose is slightly levorotatory, because the levorotatory
fructose has a greater molar rotation than the dextrorotatory
glucose.
As the sucrose is used up and the glucose-fructose mixture is formed, the angle of rotation to the
right (as the observer looks into the polarimeter tube) becomes less and less, and finally the light
is rotated to the left. The rotation is determined at the beginning (α0) and at the end of the
reaction (α∞), and the algebraic difference between these two readings is a measure of the
original concentration of the sucrose.
The reaction proceeds too slowly to be measured in pure water, but it is catalyzed by hydrogen
ions. The water is in such large excess that its concentration does not change appreciably, and
the reaction follows the equation for a pseudo-first-order reaction, even though two different
kinds of molecules are involved in the reaction.
This same reaction in biological systems is catalyzed by an enzyme called invertase. The hydrolysis
of sucrose into single sugars is necessary before the sugars can be metabolized. In humans, the
invertase enzyme is found in saliva.
Kinetics
−𝐝[𝐬𝐮𝐜𝐫𝐨𝐬𝐞]
The rate law for the inversion of sucrose is in the form: = k [sucrose]m[H2O]n[H+]p
𝐝𝐭

The concentration of water in this experiment is large and essentially constant. We will also use
a large excess of acid to maintain a constant hydrogen ion concentration. We can then rewrite
the equation to isolate the dependence on the concentration of sucrose:
−𝐝[𝐬𝐮𝐜𝐫𝐨𝐬𝐞]
= k’ [sucrose]m with k’ = k[H2O]n[H+]p
𝐝𝐭

We will assume that the reaction is first order in sucrose, m=1, which we will verify by curve
fitting to a first-order integrated rate law.
In the equations that follow we will set [sucrose] = Cs. It is assumed that the reaction goes to
completion so that practically no sucrose remains at "infinite" time. The integrated form of the
first-order-reaction differential equation is then:
𝐂𝐬
Cs = Cs0 e–k’t or ln Cs = -k’t + ln Cs0  ln = -k’t with Cs0 = [sucrose] at time 0
𝐂𝐬𝟎
𝐂𝐬
The plot ln = f(t) has the slope –k’. However, in this experiment we don't measure the
𝐂𝐬𝟎
concentration of sucrose (physical method).
Instead of measuring concentration directly, in this experiment the optical rotation, α, is
measured. Optical rotation is linear function of the concentration for each optically active
molecule in solution, Biot’s law: αi = [],T L Ci = Ai Ci ;
  = angle of rotation of polarized light (rotatory power). Dextro (+):  > 0 and Levo (-):  < 0.
 [],T = specific rotatory power (depends on the temperature and the wavelength of the light).
 L = thickness of the solution or length of the tube.
 Ci = concentration of the optically active substance i (chiral molecules in the solution)
For a solution of sucrose, glucose and fructose: α = As Cs + Ag Cg + Af Cf
And from the stoichiometry: Cg = Cf = Cs,0 - Cs
 α = As Cs + Ag Cs,0 - Ag Cs + Af Cs,0 - Af Cs
At the end of the reaction, no sucrose remains: α∞ = Ag Cg,∞ + Af Cf,∞
From the stoichiometry: Cg, ∞ = Cf,∞ = Cs,0
 α∞ = (Ag + Af) Cs,0

Likewise, at the beginning of the reaction: α0 = As Cs,0

𝛂𝟎 −𝛂∞
 α0 - α∞ = (As - Ag - Af) Cs,0  Cs,0 =
𝐀 𝐬 −𝐀𝐠 −𝐀 𝐟
𝛂−𝛂∞
 α - α∞ = As Cs + Ag Cs,0 - Ag Cs + Af Cs,0 - Af Cs - Ag Cs,0 - Af Cs,0 = (As - Ag - Af) Cs  Cs =
𝐀 𝐬 −𝐀𝐠 −𝐀𝐟
α−α∞
𝐂𝐬 As −Ag −Af 𝛂−𝛂
 ln = ln α0 −α∞ = ln𝛂 −𝛂∞ = -k’t or ln(α – α∞) = – k’t + ln(α0 – α∞)
𝐂𝐬𝟎 𝟎 ∞
As −Ag −Af

The plot ln(α – α∞) = f(t) has the slope –k’ and the y-intercept ln(α0 – α∞)
Summary: In kinetics experiments any property, such as optical rotation, that is a linear function
of concentration can be used in place of the concentration for curve fitting.

Experiment 3 – Ethyl acetate saponification (2nd order kinetic)

Purpose: The rate of reaction between ethyl acetate and OH- is followed at 2 different
temperatures by measuring the electric conductivity of the solution.
Condition: Working with ions that can transmit electricity through the solution.
Introduction
The reaction is CH3COOC2H5 + OH¯  CH3COO¯ + C2H5OH

OH- and CH3COO- are both ions or electrolyte so they can conduct electricity. Then, the kinetic of
this reaction can be studied by measuring the conductivity.
In fact, the small and very mobile ions OH- initially present in the reaction, are replaced by the
bulky and less mobile ions CH3COO-, so normally the conductivity will decrease during the
process. In addition, the conductivity is proportional to the concentration of ions by the relation:
X or κ(kappa) = Λm.C
with X or κ the specific conductance
 Λm the molar conductivity of an electrolyte
C the molar concentration of an electrolyte
At t = 0, the conductivity depends only on [OH-]0.
At any time t, the conductivity depends on both [OH-]t and [CH3COO-]t
At the end (complete reaction), the conductivity depends only on [CH3COO-]∞

Kinetics
By using an equimolar mixture of reactants:

CH3COOC2H5 + OH¯  CH3COO¯ + C2H5OH

Equimolar mixture t=0 a a 0 0
t a-x a-x x x

Knowing that the reaction is of 1st order with respect to each reactant giving an overall order 2.
−d[CH3 COOC2 H5 ] −d[OH− ]
r= = = k[CH3COOC2H5][OH¯] = k[OH¯]2
dt dt
−d[OH− ] −d[OH− ] − 𝟏 𝟏
= k[OH¯]2  = kdt  ∫ −d[OH ]
− 2 = ∫ kdt  - = kt
dt [OH− ]2 [OH ] [𝐎𝐇− ] [𝐎𝐇− ]𝟎

1 1 1 1 akt+1 𝐚 a a−a+x 𝐱
- = kt  = kt + =  = akt + 1  –1= = = akt
a−x a a−x a a 𝐚−𝐱 a−x a−x 𝐚−𝐱

[OH-]0 = a [OH-]t = a-x [CH3COO-]t = x [CH3COO-]∞ = [OH-]0 = a

X0 = Λm(OH-).[OH-]0 = Λm(OH-).a
Xt = Λm(OH-).[OH-]t + Λm(CH3COO-).[CH3COO-]t = Λm(OH-).(a-x) + Λm(CH3COO-).x
= Λm(OH-).a - Λm(OH-).x + Λm(CH3COO-).x
X∞ = Λm(CH3COO-).[CH3COO-]∞ = Λm(CH3COO-).a

 Xt - X∞ = Λm(OH-).a - Λm(OH-).x + Λm(CH3COO-).x - Λm(CH3COO-).a = (a-x)(Λm(OH-) - Λm(CH3COO-))

 a-x = (Xt - X∞)/ (Λm(OH-) - Λm(CH3COO-)) = [OH-]
 X0 - X∞ = Λm(OH-).a - Λm(CH3COO-).a = a.(Λm(OH-) - Λm(CH3COO-))
 a = (X0 - X∞)/(Λm(OH-) - Λm(CH3COO-)) = [OH-]0
𝐚 (𝐗𝟎 − 𝐗∞)/(𝚲𝐦(𝐎𝐇−) − 𝚲𝐦(𝐂𝐇𝟑𝐂𝐎𝐎−)) 𝐗𝟎 − 𝐗∞
= akt + 1  (𝐗𝐭 − 𝐗∞)/ (𝚲𝐦(𝐎𝐇−) − 𝚲𝐦(𝐂𝐇𝟑𝐂𝐎𝐎−)) = = akt + 1
𝐚−𝐱 𝐗𝐭 − 𝐗∞
 𝟏 𝐚𝐤𝐭 𝟏
= -
𝐗 𝐭 −𝐗 ∞ 𝐗 𝟎 −𝐗∞ 𝐗 𝟎 −𝐗∞

Experimentally, we measure the conductivity Xt during the process, we measure also the
conductivity X0 at t = 0 when we mix both reactants together and at the end of the reaction X∞
𝟏
when we are sure that the reaction has finished. Then, by plotting = f(t), an increasing
𝐗 𝐭 −𝐗 ∞
𝟏
straight line is obtained with [OH-]0k as a slope and as a y-intercept.
𝐗 𝟎 −𝐗 ∞

Also, by working at 2 different temperatures we can find 2 different rate constants leading to
𝐤𝟐 𝑬𝒂 𝟏 𝟏
calculate the activation energy of this reaction: ln = ( - )
𝐤𝟏 𝑹 𝑻𝟏 𝑻𝟐

Experiment 4 – Oxidation of iodide ions by the peroxodisulfate ions (pseudo 1st order kinetic)
Purpose: The rate of reaction between I- and S2O82- is followed by measuring the absorbance of
the solution. The effect of Cu2+ ions on the rate of this reaction is also studied.

Condition: Working with colored species that can absorb light.

Introduction
The reaction is S2O82 + 2I–  2SO42 + I2
I2 is yellow, it is the only species that can absorb light in this reaction; so we can study the kinetics
by measuring the variation in the absorbance using a spectrophotometer.

The absorbance of a species is related to its concentration through the Beer-Lambert law:

A = εlC
 ε: extinction coefficient or absorptivity constant ([Link]-1)
 l: length of the cuvette, usually 1cm
 C: concentration of the absorbing species (mol.L -1)

At t = 0, there is no absorbance (no colored reactants); A = 0

At any time t, the absorbance depends on [I2]t ; At = εl[I2]t
At the end (complete reaction), the absorbance depends only on [I2]∞ ; A∞ = εl[I2]∞

Kinetics
This reaction is of first order with respect to each reactant.
If we use a large excess of I-, its concentration almost will not change [I -]0 ≈ [I-]t ≈ constant.
 S2O82 + 2I–  2SO42 + I2
t=0 a b 0 0
t a-x b 2x x
−d(a−x) dx
r= = = k(a-x)b = k’(a-x) with k’ = kb
dt dt
𝑑𝑥 𝐚
∫ 𝑎−𝑥 = ∫ 𝑘′𝑑𝑡  ln(a-x) = -k’t + lna or ln = k’t
𝐚−𝐱

[S2O82-]0 = [I2]∞ = a [S2O82-]t = a-x [I2]t = x

𝐀∞
A∞ = εl[I2]∞ = εla  a =
𝛆𝐥
𝐀 ∞ −𝐀𝐭
A∞ - At = εl[I2]∞ - εl[I2]t = εla – εlx = εl(a-x)  a-x =
𝛆𝐥
𝐴∞
𝐚 εl
𝐀∞
ln 𝐚−𝐱 = ln 𝐴∞−𝐴𝑡 = ln = k’t or ln(A∞-At) = -k’t + lnA∞
𝐀∞ −𝐀𝐭
εl

Experimentally, we measure the absorbance of I 2 At during the process, we measure also the
absorbance A∞ at the end of the reaction (using a catalyst Cu2+). Then, by plotting ln(A∞-At) = f(t),
a decreasing straight line is obtained with –k’ as a slope and lnA∞ as a y-intercept.
Knowing precisely [I-]0, we calculate the rate constant k from the pseudo rate constant k’:
𝐤′
k=
[𝐈− ]𝟎

N.B. The average time of this reaction is about ½ hour at room temperature, it is therefore
necessary to handle quickly and carefully to have 10 measures between instant zero and the end
of the reaction.
Experiment 5 – Influence of the reactants concentration on the rate
Purpose: Study by a chemical method (titration) the effect of the concentration of
peroxodisulfate (S2O82-) on the rate of the between I- and S2O82- (same reaction as experiment 4),
and to find the rate expression and the order of this reaction.

Condition: titration must be carried out quickly compared to the speed of the studied reaction.
Introduction
The reaction is S2O82 + 2I–  2SO42 + I2

We know that the rate is related to the concentration of reactants: r = k(T)[ S2O82]α[ I–]β
Kinetics
In order to study the effect of [ S2O82], [ I–] should remain constant.
The rate expression becomes: r = k’[ S2O82]α with k’ = k[ I–]β
Experimental determination of the rate for different concentrations of peroxodisulfate allows to
check the previous expression, to determine the order α with respect to peroxodisulfate and
calculate the rate constant k’ then k.
Rate determination can be done by finding the time required so that N moles of diiodine are
formed. For this we add, in advance, in the middle reaction a fixed quantities of sodium
thiosulfate S2O32 which reacts with the diiode according to the reaction:

2S2O32 + I2  2 I + S4O62

This reaction is very rapid, and it regenerates the iodide ions I. The concentration of I is then
constant throughout the reaction.

When the reaction starts there is formation of I 2:

S2O82 + 2I–  2SO42 + I2
But the presence of S2O32- at the beginning will
eliminate I2: 2S2O32 + I2  2 I + S4O62

For this reason, no yellow coloration, due to I2,

appears until the time t, when the effect of the
2mL of S2O32- has ended. At this moment, 2 new
mL are added. The yellow coloration disappears.

The cycles (yellow/colorless) is repeated many times. By knowing what N moles of I2 represents
the added quantity of S2O32, and the time needed for yellow coloration to reappear each time;
the N / t ratio represents the average rate of iodine formation.

After each cycle, the quantity of the reactant S2O82- will decrease and the time needed to the
yellow coloration to reappear will increase (rate will decrease); then the rate and the
concentration of reactants are proportional.
Experiment 6 – Thermal decomposition of Phenyldiazonium Chloride 1st order kinetic

Purpose: Determination of the rate constant of the phenyldiazonium chloride’s decomposition

reaction, by measuring the volume of a gas released during the reaction, using a nitrometer.

Condition: At least, one of the products must be a gas.

Introduction

Decomposition reaction in water: C6H5N2Cl(l) + H2O(l)  C6 H5OH(l) + HCl(l) + N2(g)

N2 is gas, the progress of this reaction can be followed by measuring the volume of nitrogen
released, at determined time intervals, using a nitrometer.

We use a large excess of water compared to C6H5N2Cl. ([H2O]0 ≈ [H2O]t ≈ constant)

Kinetics
C6H5N2Cl(l) + H2O(l)  C6 H5OH(l) + HCl(l) + N2(g)
t=0 a b 0 0 0
t a-x b x x x

This reaction is of 1st order with respect to each reactant (overall order 2); because water is in
large excess, the rate becomes of pseudo-first order:

dx
r= = k(a-x)(b-x) = kb(a-x) = k’(a-x)
dt

dx 𝐚
∫ a−x = ∫ k′dt  ln(a-x) = -k’t + lna  ln 𝐚−𝐱 = k’t

𝐕∞
[N2]∞ = [C6H5N2Cl]0 = a  V∞ = n(N2)∞ Vm = [Link]  a =
𝐕.𝐕𝐦
𝐕𝐭 𝐕∞ −𝐕𝐭
[N2]t = x  Vt = n(N2)t Vm = [Link]  x =  a-x =
𝐕.𝐕𝐦 𝐕.𝐕𝐦

Vt : volume of N2 released at time t V∞: volume of N2 released at the end of the reaction

V: volume of the system (flask + burettes) Vm: molar volume

𝐕∞
𝐚 𝐕.𝐕𝐦 𝐕∞
ln = ln 𝐕∞ −𝐕𝐭 = ln 𝐕 −𝐕 = k’t  ln (𝐕∞ − 𝐕𝐭 ) = -k’t + ln 𝐕∞
𝐚−𝐱 ∞ 𝐭
𝐕.𝐕𝐦

Experimentally, we read the released volume every 1 minute then we plot ln (V∞ − Vt ) = f(t); the
obtained graph is a decreasing straight line, with –k’ as a slope and ln V∞ as a y-intercept.