Reaction Rates and Equilibrium

Spontaneity
Reaction Rates
Equilibrium
Thermodynamics vs. Kinetics
Thermodynamics:
Energy of Reaction
Spontaneity of
Reaction
Kinetics:
Speed of Reaction
Equilibrium
We begin with Thermodynamics...
Enthalpy (H) is PART of the
story...
All processes prefer to lower energy
(enthalpy) (minimize enthalpy)
Such processes release energy, usually as
heat
These processes are exothermic
However, endothermic process also
occur, so there must be something else
driving reactions as well
Enthalpy arises because of
changes in bonding
Before a reaction can proceed, we must
break the bonds of the reactants; this always
costs energy
At the end of the reaction, new bonds have
formed in the products; this always returns
energy
If we have more energy return than the
initial cost, the reaction is exothermic
ENTROPY (S); the rest of the
story
Often thought of as disorder or randomness;
the more random, the higher the entropy
Better thought of as information theory: the
higher the entropy, the more that we do not
know about the system
Processes tend to prefer to increase
(maximize) entropy, but some processes
lower entropy
We can often predict entropy
changes
Any process which results in a less
condensed phase increases entropy
Any reaction resulting in the formation of
products in a less condensed phase can be
expected to increase entropy
Any reaction that has more products than
reactants can be expected to increase
entropy
Gibbs Free Energy:
The Relationship between Entropy and Enthalpy
The reaction is spontaneous (Exergonic) when
Gibbs Free Energy is negative
The reaction is non-spontaneous (Endergonic)
when Gibbs Free Energy is positive
G H T S =
Implications of Spontaneity
H S G
+ + + or -:
spontaneous
at high T
+ - + : NEVER
spontaneous
- + - : ALWAYS
spontaneous
- - + or -:
spontaneous
at low T
Kinetics
Just because a reaction will occur is no
guarantee that it will happen in a short
enough period of time for us to notice it
How quickly a reaction occurs is kinetics
Reaction rates can be measured as a
function of how quickly the concentration
of a reactant or product changes in time
Rate Equation
Rate
C
t
=

The determining factor in reaction

rates is the Rate Mechanism
A rate mechanism is a series of simple
chemical steps that add up to the overall
reaction
What must happen for a reaction to occur?
Reactants and products must come in contact
(collide)
Old bonds must be broken (internal energy
increases)
New bonds form (internal energy decreases)
Favorable Collisions
Only two molecules can collide
simultaneously
Collisions must occur in the correct
orientation
Collisions must have correct energy
Too slow: not enough energy to overcome
activation energy
Too fast: not enough time to react (glance off
each other)
Exothermic Energy Diagram
Endothermic Energy Diagram
Activation Energy
Activation energy is the amount of energy
necessary to start the reaction; that is, the
minimum energy necessary to break the
bonds of the reactants
The higher the activation energy, the slower
the reaction
Reversible Reactions
Many reactions can occur in two directions;
reactant to product, and product to reactant
These are reversible reactions
By convention, reactants are always on the right
H O l CO g H CO aq
2 2 2 3
( ) ( ) ( ) +
Reversible Reaction Facts
Reactants always on the left, products on
the right
Forward reaction: Reactants to Products
Reverse direction: Products to Reactants
If a reaction is exothermic in the forward
reaction, it is equally endothermic in the
reverse reaction
Direction of reaction is at the discression of
the person writing the equation
Factors that influence reaction
rates
Nature of reactants
Reactant concentrations
Temperature
Catalysts...
Catalysts act by lowering the
activation energy barrier
A catalyst lowers the
activation energy
barrier by providing a
new reaction pathway
It increases both the
forward and backward
reaction in a reversible
reaction equally
Catalysts do not
change the energy of
reaction
Equilibrium
If reactions can proceed in both the forward
and reverse directions, they must reach
equilibiumconcentrations
At this point, none of the concentrations are
changing anymore
Concentrations are not (necessarily) equal at
this point; just stable
Equilibrium and Kinetics
Equilibiumis a kinetic thing; the reactions
do not stop, they just occur in each direction
at the same rate
kinetics tells us that reaction rates are a
function of reactant concentrations
therefore, reaction will be in equilibrium
when the concentrations of the reactants and
products are such that the rate of the
forward and reverse reactions are equal
Equilibrium Constant
For any given reversible reaction under specific
conditions, there is a constant that expresses the
ratio of reactants and product concentrations at
equilibrium.
[ ] [ ]
[ ] [ ]
aA bB cC dD
K
C D
A B
eq
c d
a b
+ +
=
Factors Influencing Equilibrium
What CAN affect
equilibrium?
Temperature
Pressure (only if gases
are involved)
Concentrations
What CANNOT affect
equilibrium?
Catalysts (increases
rates of both directions
equally)
LeChatleiere: My Favorite
French Dude!
LeChatliers Principle: If a stress is applied
to a system, that system will respond so as
to relieve that stress
Temperature
Concentration
Pressure
In equilibrium, we can influence which side
of the reaction we favor by changing
conditions appropriately
LeChatlier : Some Examples
Increase T: Favor endothermic side (absorb
new heat)
Increase P: Favor side with fewer moles of
gas (decrease excess P)
Add chemical: Push reaction to remove
chemical
Remove chemical: Pull reaction to replace
chemical