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INTRODUCTION
INTRODUCTION
Acids and bases are classified in different ways o Based on taste and feel
INTRODUCTION
LEWIS CONCEPT
A Lewis acid is a substance that acts as an electron
pair acceptor. A Lewis base is a substance that acts as an electron pair donor.
C
Rate constant
k4 k3
k1 k2
/[A]eq
INTRODUCTION
Reaction to be studied
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
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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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 colors of the mixtures at the start of mixing and after 30 minutes of mixing were noted.
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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
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
Lower temperature, short reaction time (a) Higher temperature, short reaction time (b) Lower temperature, long reaction time (c)
(a)
(b)
(c)
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
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 (%)
113.09
31.91
132.97
42045.17
14.95
99.92
3.47
5.85
132.97
42045.17
97.39
99.99
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
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
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
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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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