QUESTION OF THE
DAY…..
QUESTION OF THE DAY: A PARTICULAR PHARMACEUTICAL
DRUG FOLLOWS FIRST ORDER KINETICS IN THE HUMAN BODY.
HOW MUCH OF THE DRUG REMAINS AFTER 23.0 MINUTES IF
IT HAS A RATE CONSTANT EQUAL TO .0173/MIN, AND THE PILL
TAKEN BY THE INDIVIDUAL IS 200.0 MG? ASSUME THE PILL
CONTAINS 100% OF THE DRUG. ALSO ASSUME THAT THE
CONCEPTUAL REACTION TAKING PLACE IN THE BODY IS:
ACTIVE DRUG → INACTIVE DRUG
TEMPERATURE AND
RATE
• Generally, as the temperature of a
chemical reaction increases, so
does the reaction rate, and
therefore, so does the k, or rate
constant.
• This is because k is temperature
dependent.
• Again – the k, or rate constant,
indirectly tells me how fast or slow
a reaction will proceed!
THE COLLISION THEORY MODEL
• In a chemical reaction, bonds are broken
and new bonds are formed.
• Molecules can only react if they collide
with each other in the right
orientation!
THE COLLISION THEORY MODEL
In order to successfully react:
1. Molecules must collide
2. Molecules must have the correct orientation with one another
3. Molecules must collide with enough energy to cause bond breakage (known as the activation energy, or Ea)
These molecules must have enough kinetic energy or
Notice the orientation of the two
activation energy (Ea) in order to collide, and force
existing bonds to break and new bonds to form! molecules about to bond…the two
atoms that will form the new bond
are facing each other!
Before Collision During Collision After Collision
2 NO + Cl2 → 2 NOCl
NO + O3 → NO2 + O2 + 199.8 kJ
MAXWELL–BOLTZMANN DISTRIBUTION
• The Maxwell-Boltzmann distribution equation, which forms the basis of the kinetic theory of gases, defines
the distribution of speeds for a gas at a certain temperature.
• Temperature is defined as a measure of the average kinetic energy of the molecules in a sample.
• At any temperature, there is a wide distribution of molecules with different kinetic energies.
• If the dotted line represents the activation energy, as the temperature increases, so does the fraction or
number of molecules that can overcome the activation energy barrier and react.
• Why? At higher temperatures, the frequency of high energy collisions increases, because there are more
molecules that have a high enough kinetic energy to collide successfully!
• As a result, the reaction rate increases, and so does the rate constant at that temperature!
Fraction of molecules
that can overcome
the activation energy
barrier and react!
MAXWELL–BOLTZMANN DISTRIBUTION
This fraction of molecules that have enough energy to react can
be found through the expression:
-Ea/RT
f=e
where Ea is the activation energy required to initiate the reaction,
R is the gas constant (8.314 J/mol K) and T is the temperature
in Kelvin .
ARRHENIUS EQUATION
Svante Arrhenius developed a mathematical relationship between k and Ea using
the Boltzmann expression:
-Ea/RT
k = Ae
where A is the frequency factor, a number that represents the likelihood that
collisions would occur with the proper orientation for reaction.
A = pZ, where:
p = fraction of collisions with proper orientation
Z = collision frequency
(A changes slightly with temperature, as one would
expect from collision theory, but not by much! It is usually
ignored, as k changes proportionally with T)
So – for a reaction to be successful, there must be enough collisions
that have both sufficient energy to overcome energy barriers, AND
correct orientations that allow the bonds to rearrange in the correct
orientation to make product!
SUMMARY OF KINETIC EQUATIONS
Zero Order First Order Second Order
Instant Rate Rate = Rate = k[A]1 Rate = k[A]2
Equation (Differential
Rate Law)
k[A]0
Time Based Rate [A]t = -kt + ln [A]t = -kt + ln
Equation (Integrated 1 = kt + 1
Rate Law) [A]i [A]i
[A]t
[A]i
Slope of Line -k -k k
Half-Life
t1/2 = [A]i t1/2 = .693 t1/2 = 1
2k k k[A]i
Arrhenius Equation
ln (k) = - Ea + ln A Ln k2 = Ea • 1 -