Exercise 5

INTRODUCTION

C
Rate constant

k4 k3

k1 k2

If k1 > k3, formation B is favored since higher k

means higher rate

Equilibrium constant If k3 / k4 > k1 / k2 , formation of C is favored since

the Keq of C is greater

Note: k3 / k4 = [C]eq / [A]eq and k1 / k2 = [B]eq

/[A]eq

INTRODUCTION
Reaction to be studied

(yellow) kineticallycontrolled product

(orange) thermodynamically -controlled product

INTRODUCTION
Objectives 1. to construct progress curves for the reaction scheme

demonstrating kinetic vs. thermodynamic control; 2. to calculate equilibrium constants and Gibbs free energies for the reaction scheme using the Monte Carlo method; and 3. to observe the effect of reaction time and reactant concentration on the kinetics and thermodynamics of the isomerization of mercuric iodide.

METHODOLOGY

METHODOLOGY- Monte Carlo Method

The reaction scheme selected in the dialog box was the kinetic vs. thermodynamic control button (or reaction 5).

The program for Monte Carlo Method for Kinetics was used

The necessary values were inputted namely: activation energies, initial number of molecules, sampling parameters, number of cycles and temperature
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METHODOLOGY- Experimental Method

50 ml of each of the following solutions were prepared: 0.05 M and 0.00625 M ; 0.10 M and 0.0125 M KI.

25 mL of the solutions was placed (concentrated and dilute) separately in 100 mL beakers and stirred using a magnetic stirrer.

Each of the KI solutions was added (concentrated and dilute) to the solutions.

The observations were recorded.

The colors of the mixtures at the start of mixing and after 30 minutes of mixing were noted.

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RESULTS AND DISCUSSION

RESULTS AND DISCUSSION

Isomerization of mercuric iodide

(yellow) kineticallycontrolled product

(orange) thermodynamically -controlled product

RESULTS AND DISCUSSION

tetragonal structure - thermodynamically-controlled

structure

more ordered structure requires a longer time for the molecules to rearrange this way, takes a longer time for it to be formed also the arrangement with lower energy

rhombic structure kinetically-controlled structure has a more random arrangement of molecules easier to form when molecules collide takes less time for it to be formed Structure with the higher energy

RESULTS AND DISCUSSION

Monte Carlo method

refers to a broad class of algorithms that solve problems through the use of random numbers a computational method which employs probability to study kinetics of a reaction

Progress curves were generated at different conditions

Lower temperature, short reaction time (a) Higher temperature, short reaction time (b) Lower temperature, long reaction time (c)

Progress Curves plots of number of molecules vs. number of cycles or time

(a)

(b)

(c)

RESULTS AND DISCUSSION

Number of molecules become constant over time

Corresponds to equilibration Can be used to obtain equilbrium concentrations of A , B, and C and be used to calculate the equlibrium constants

RESULTS AND DISCUSSION

Table 5.2 Values of and at different conditions for the reaction scheme of mercuric iodide. Condition Lower temp, short rxn time Higher temp, short rxn time Lower temp, long rxn time

113.09 3.47 177.20

31.91 5.85 1822.20

1st condition K12>K34; kinetically controlled product is favored nd condtion K 2 34 > K12; thermodynamically controlled product is favored rd 3 condition - K34 > k12; thermodynamically controlled product is favored

Calculation of rate constants using Arrhenius equation

Repeat steps for k3 / k4

Working equation

Values were compared with the values obtained using the progress curves

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Table 5.3 Values of the ratios of rate constants and comparison with the equilibrium constants
From progress curves Condition Using Arrhenius eqn. Percent difference (%)

Lower temp, short rxn time

Higher temp, short rxn time

113.09

31.91

132.97

42045.17

14.95

99.92

3.47

5.85

132.97

42045.17

97.39

99.99

Lower temp, long rxn time

177.20

1822.20

132.97

42045.17

33.27

95.67

Percent differences may be accounted by the inherent errors of the Monte Carlo method

Values of Gibbs free energy were also obtained

Gibbs free energy

allows us to represent the spontaneity of a process in terms of the properties of the system.

Working equation

Table 5.4 Values of the Gibbs energy calculated using the progress curves and the Arrhenius equation.
From progress Using Arrhenius eqn. curves Percent difference (%)

Condition

Lower temp, -32525 short rxn time 31448 23033 Higher temp, -8283 -11754 -32525 short rxn time Lower temp, -32525 long rxn time 34435 49936

-70812 -70812

3.31 74.53

67.47 83.40

-70812

5.87

29.48

The values of G calculated agree with the values of K obtained earlier

1st condition G12 < G34; reaction towards the kinetically-controlled products is more spontaneous 2nd condition and 3rd condition G34 < G12; the reaction towards the thermodynamically-controlled product is more spontaneous.

Experimental Method

Experimental study of the effect of concentration and time on the isomerization of mercuric iodide

Table 5.5. Data table for the observations in the experimental method.
COLOR OF MIXTURE MIXTURE Conc. KI + Dilute KI + Immediately After Mixing Peach Yellow After 30 minutes Dark orange Lighter shade of dark orange

(a)

(b)

(c)

(d)

Effect of Concentration
Mixture of concentrated solutions orange

thermodynamically-controlled product was formed

Mixture of dilute solutions yellow

kinetically-controlled product was formed

 Effect of Temperature Immediately after mixing yellow

kinetically-controlled product was formed

3o minutes after mixing orange

thermodynamically-controlled product was formed

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 Generalizations
formation of the kinetically-controlled product is favored by short reaction time and low concentration Can be accounted by its lower Ea formation of the thermodynamically-controlled product is favored by high temperature, long reaction time and high concentration Can be accounted by its more negative G

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Source of error/ recommendations The percent differences in the calculations can be accounted by the inherent errors of the Monte Carlo method. Hence, no simple correction can be recommended.

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