Physical Chemistry II Essentials
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Physical Chemistry II Essentials - The Editors of REA
MOLECULES
CHAPTER 15
REACTION MECHANISMS
15.1 MECHANISM OF A REACTION
The mechanism of a reaction is the path that the reaction takes. The following sequence of reactions is the mechanism of the reaction
Each of the above intermediate reactions is an elementary reaction. Molecular events are described by the elementary reactions.
The rate equation for a complex mechanism is the sum of the rate equations for the simple reactions composing it.
15.2 OPPOSING REACTIONS AND EQUILIBRIUM CONSTANTS
The rate equation for the first order reaction
is
where
k1 = the forward rate constant
k_1 = the reverse rate constant.
and
where K is the equilibrium constant and is known as principle of Guldberg and Waage, or the law of mass action.
where
where
, the rate equation is
where
where
The principle of detailed balancing assumes that the rate of an elementary process is equal to the rate of the reverse process at equilibrium. The principle of detailed balancing is an extension of the principle of microscopic reversibility, which states that all the momenta (both translational and internal) are reversed when two molecules collide and then the system returns by the same process in the reverse direction.
15.3 CONSECUTIVE AND PARALLEL REACTIONS AND STEADY STATE
CONSECUTIVE REACTIONS
For the consecutive first-order reactions,
the concentrations at time t are
For the two consecutive reversible reactions,
at equilibrium
Parallel reactions
For the parallel reactions
rate = k1CACB + k2CACB + k3CACB = kCACB where
k = k1 + k2 + k3
STEADY STATE
The steady state approximation is the assumption that the reactive intermediate substances are at constant concentrations as the reaction takes place.
For the reactions
15.4 COMPLEX REACTIONS
. A chain reaction is the sequence of reactions, in the gas phase, of radicals producing radicals.
The chain reaction is analyzed by the following steps:
Initiation step, in which normal molecules form radicals. Example:
Propagation step, in which the free radicals attack other molecules to produce new radicals. Example:
Inhibition step, in which the radical attacks the product molecule. Example:
Termination step, in which the chain of radical reactions ends. Example:
CHAPTER 16
THEORETICAL APPROACHES TO CHEMICAL KINETICS
16.1 TEMPERATURE DEPENDENCE OF REACTION RATE
The reaction rate increases as the temperature increases. For every 10°K increase in temperature, the reaction rate doubles. The rate constant is related to the temperature by the following Arrhenius equation:
where
k = the rate constant
A = the frequency factor or the pre-exponential factor
Ea = the activation energy
T = the temperature in °K.
where K is the equilibrium constant and ΔE is the change in energy.
Fig. 16.1 Arrhenius plot that shows the relationship between the rate constant and the temperature.
16.2 THE COLLISION THEORY
The collision theory postulates that in order for molecules to interact, they must approach each other so closely that they can be said to be in collision. The speed of reaction is equal to the number of collisions per second times the fraction of the collisions that are effective in producing chemical change.
The collision between like molecules is
where
= the average velocity
n*= the number of gas molecules per cubic centimeter
m = the mass
d = the diameter of the molecules
ZAA = the collision frequency.
The collision between unlike molecules is
where
nA* and nB* = the concentrations of A and B
dAB = the average of the two diameters (or the sum of the molecular radii )
= the collision cross section which corresponds to the area of the molecules for a