Reaction Rates & Equilibrium

Spontaneous and Nonspontaneous Changes Reaction Rates Molecular Collisions Energy Diagrams Factors Affecting Reaction Rates Chemical Equilibrium Factors that Influence Equilibrium

Reaction Rates and Equilibrium

This chapter considers three factors. Thermodynamics If a reaction will occur. Kinetics How rapidly a reaction will occur. Equilibrium How much of a reaction will occur.

Spontaneous & nonspontaneous changes

Spontaneous process Takes place naturally with no apparent cause or stimulus. Nonspontaneous process Requires that something be done in order for it to occur.

When will a reaction be spontaneous?

Spontaneity of a reaction can be determined by a study of thermodynamics. It can be used to calculate the amount of useful work that is produced by some chemical reactions. It also shows the two competing factors that determine the spontaneity of a reaction. Enthalpy and Entropy

Spontaneous

Nonspontaneous

First law of thermodynamics

Energy can neither be created nor destroyed in a chemical reaction

Energy and chemical bonds

During a chemical reaction
Old bonds break. New bonds are formed. Energy is either consumed or produced.
Exothermic Energy is released. New bonds are more stable. Endothermic Energy is required. New bonds are less stable.

Energy can only be converted between forms. Bonds can be viewed as potential energy. Heat associated with a reaction is called
enthalpy.

!H

Exothermic
Reactants

Endothermic
Products

Energy

Products Since excess energy is released, the products are more stable.

Energy

Reactants
Additional energy is required so the products are less stable.

Enthalpy
This change in energy is called enthalpy.

Second law of thermodynamics

A system and its surroundings spontaneously tend towards increasing disorder Entropy - the degree of disorder in a system.

!H = Hproducts - Hreactants
You must look at all of the reactants and products to determine the !H. !H > 0 reactants are more stable !H = 0 neither are more stable !H < 0 products are more stable This factor is only part of the picture.

!S = Sproducts - Sreactants
Things tend to break down and become more random.

Example
Which of the following would you expect to have a higher entropy? Rock Soil Adults bedroom Teenagers bedroom Ice Water Clouds Rain Pure Water Saline Old tired men Young dedicated students

Effect of state on entropy

Solid
Gas

Which has higher entropy?

Enthalpy vs. Entropy

Two competing forces. Enthalpy
Stability gained from being ordered.

Free energy - G
The maximum amount of energy that can be obtained from a reaction. The total change in free energy is then

Entropy
Stability gained from being random. Both affect how a reaction will proceed. We need a term that considers both factors.

!G = Gproducts - Greactants
At constant pressure

!G = !H - T !S
Gibbs

Free energy
The sign of !G tells us a lot about the reaction !G > 0 Not spontaneous, requires energy to occur. !G < 0 Spontaneous, will occur on its own, releasing energy. !G = 0 (!H = T!S) At equilibrium, no desire to go one way or the other - why reactions stop at some point.

Chemical kinetics
The study of reactions as a function of time. !G Only tells us if a reaction will occur but not how long it will take. Kinetics Measures the time required for areaction to occur. Example - Diamonds Less stable than graphite but very slow kinetics.

Chemical kinetics
Kinetics of a chemical reaction can tell us

Effective collisions
For reactants to make products They must collide.

how chemicals react to form products

(mechanism).

The energy of collision must be greater

than the bond energy between the atoms Activation Energy The minimum amount of energy required to produce a chemical reaction.

how long it will take for a reaction to reach

completion.

effects of catalysts and enzymes. how to control a reaction.

Effective collision
Activated Complex

Energy diagrams
This type of plot shows the energy changes during a reaction.

Energy

A temporary state where bonds are in the process of reforming.

!H

activation energy

Examples of energy diagrams

Examples
High activation energy Low heat of reaction

Exothermic reaction

Low activation energy High heat of reaction Endothermic reaction

Factors that influence reaction rates

Can be affected by reactant structure concentration of reactants temperature physical state of reactants presence of a catalyst Can be used to describe an equilibrium - process that is established when the rate of the forward reaction is equal to the reverse reaction.

Catalysis
Catalyst A substance that changes the rate of a reaction without being used in the reaction. Provides an easier way to react. Lower activation energy. Still make the same products. Enzymes are biological catalysts. Inhibitor A substance that decreases the rate of reaction.

Catalysis
Types of catalysts Homogeneous - same phase Catalyst is uniformly distributed throughout the reaction mixture Example - I- in peroxide. Heterogeneous - different phase Catalyst is usually a solid and the reactants are gases or liquids Example - Automobile catalytic converter

Catalysts
Work by altering the mechanism of a reaction. The net effect is to reduce the activation energy.

Uncatalysed reaction

Catalysed reaction

Catalysts
All that matters is that the reaction goes from the reactants to the products. It does not matter how you get there.
Im in static equilibrium.

Equilibrium

A + B

AB

AB* + C

A+B+C
Reactants Products

Catalyst

Dynamic Equilibrium

A state where the forward and reverse conditions occur at the same rate.

Equilibrium and reaction rates

A point is ultimately reached where the rates of the forward and reverse reactions are the same.

Equilibrium
Concentration

Reaction rate

Kinetic region

Equilibrium region

Time

At this point, equilibrium is achieved.

Time

Chemical equilibrium
A dynamic process on the molecular level achieved when concentration of reactants and products remain constant over time. for a physical process: H2O(l) (reactant) H2O(s) (product)

Equilibrium constant (K)

We can write an equilibrium expression for any reaction at constant temperature.

aA + bB

cC + dD

Keq =

[C]c [D]d [A]a [B]b

the equilibrium process is indicated with an equilibrium arrow

[ ] represents the molar concentrations - mol/L Always put products over reactants and raise each to the power of their coefficients.

Le Chateliers principle
Any stress placed on an equilibrium system will cause the system to shift to minimize the effect of the stress.
You can put stress on a system by adding or removing something from one side of a reaction. N 2 + 3 H2 2 NH3

Le Chateliers principle
N 2 + 3 H2 2 NH3

[ NH3 ] 2 Keq = [ N2 ] [ H 2 ] 3
Adding ammonia - shift to left Adding nitrogen - shift to right

What effect will there be if you added more ammonia? How about more nitrogen?

Example O2 transport in blood

Equilibrium equation
Hb + 4 O2 Hb(O2)4

O2 transport
Equilibrium equation

Hb + 4 O2
Equilibrium expression
KHb =

Hb(O2)4

Equilibrium expression KHb = [Hb(O2)4] [Hb] [O2]4

[Hb(O2)4] [Hb] [O2]4

O2 transport
In the lungs there is an abundance of O2 so: Hb + 4 O2 Hb(O2)4 Oxygen is picked up by the hemoglobin. When blood reaches the cells, there is a lack of O2 so: Hb + 4 O2 Hb(O2)4 Oxygen is given up by the hemoglobin.

Le Chateliers principle
Lets say that

KHb =

[Hb(O2)4] [Hb] [O2]4

= 5.0 x105

The ratio of oxygenated to unoxygenated hemoglobin is:

KHb x [O2]4 =

[Hb(O2)4] [Hb]

Le Chateliers principle
If the solubility of O2 in blood at 37oC = 0.1M. (in the lungs) [Hb(O2)4] KHb x [O2]4 = = 5.0x105 x 0.14 [Hb] = 50 In the capillaries, the O2 level is about 0.001M so [Hb(O2)4] KHb x [O2]4 = = 5.0x105 x 0.0014 [Hb] = 5.0 x 10-7

Le Chateliers principle
Pressure will affect an equilibrium with gases as reactants or products. 3 H2(g) + N2(g) 4 mol of reactants 2 NH3(g) 2 mol of products

Increasing pressure causes the equilibrium to shift to the side with the least moles of gas.

Le Chateliers principle
Heat will also affect an equilibrium NaOH(s) Na+(aq) + OH-(aq) + heat

Increasing the temperature causes less NaOH to dissolve.