Reaction Rates and Chemical Equilibrium

Activated Complex

Activation Energy is being supplied

Collision Theory


Reactions can occur:

  

Very fast such as a firecracker Very slow such as the time it took for dead plants to make coal Moderately such as food spoilage

 

A rate is a measure of the speed of any change that occurs within an interval of time In chemistry, reaction rate is expressed as the amount of reactant changing per unit time. Example: 3 moles/year, or 5 grams/second

I wonder what happens if I mix these two solutions

WOW, that was really FAST

It was also really FUN

I wonder if I should be wearing my goggles?

I. Reaction Rates
A. Collision Model: molecules, ions or atoms must touch (or collide) to react
However, only a small fraction of collisions produces a reaction. Why?

1. Particles lacking the necessary KE to react will bounce apart unchanged

Negative/positive ions repeling each other, e- clouds repel each other strongly at short distances Ions/molecules with very high KE can overcome repulsive forces to get close enough to react particles must hit in the correct orientation of e- clouds

2. Collisions must have enough energy to produce the reaction: must equal or exceed the activation energy - the minimum energy needed to react.

 Will a AA battery start a car? Think of clay clumps thrown together gently they dont stick, but if thrown together forcefully, they stick tightly to each other.

3. An activated complex is an unstable arrangement of atoms that forms momentarily (typically about 10-13 seconds) at the peak of the activation-energy barrier


This is sometimes called the transition state

a. Results in either a) forming products, or b) reformation of reactants



Both outcomes are equally likely

- Page 543
a. Reactants b. Absorbed c. No; it could also revert back to the reactants

The collision theory explains why some naturally occurring reactions are very slow


Carbon and oxygen react when charcoal burns, but this has a very high activation energy (C + O2(g) C CO2(g) + 393.5 kJ) At room temperature, the collisions between carbon and oxygen are not enough to cause a reaction

Mechanisms and Rates

 

Most reactions are several elementary steps Reaction progress curve for complex reactions is several peaks and valleys


Peaks are specific step activation energy and valleys are energy of intermediate products

There is an activation energy for each elementary step. Slowest step (rate determining) must have the highest activation energy.

+
Ea First step is fast Low activation energy

+
Ea

Second step is slow High activation energy

+
Ea

Third step is fast Low activation energy

Second step is rate determining

Intermediates are present

Activated Complexes or Transition States

Reaction between  ethene, CH2=CH2, and hydrogen chloride, HCl  Produces chloroethane After two molecules collide  A double bond between the two C is converted into a single bond  A H atom gets attached to one of the C  and a Cl atom to the other  The reaction can only happen if the hydrogen end of the H-Cl bond approaches the C-C double bond HC-

What happens in the collision process?

(a) Two BrNO molecules approach each other at high speeds. (b) The collision occurs. (c) The energy of the collision causes Br-N bonds to break and bonds to form. (d) The products: one Br2 and two NO molecules.

Br-Br

Reaction progress of two BrNO molecules terms of energy

B. Factors Affecting Rate

1. Temperature
Higher temp. faster particles More and harder collisions

2. Surface Area (Particle size)

Smaller particles bigger surface area

3. Concentration
Increasing conc. USUALLY increases rate More concentrated closer together the particles Collide more often Faster reaction

4. Dissolving speeds up reactions.

Getting two solids to react w/each other is slow.

5. Catalysts- substances that speed up a reaction without being used up (enzyme)

Speeds up rxn by giving the rxn a new path new path has a lower activation energy More molecules have this energy The reaction goes faster only aids reactions that are thermodynamically possible

a. Inhibitor- a substance that blocks a catalyst; rxns slows or even stops

Endothermic Reaction with a Catalyst

Exothermic Reaction with a Catalyst

C. Heterogeneous Reactions: reactants in Reactions: different phases 1. Homogeneous Reactions only one phase for reactants & products

Heterogeneous Catalysis
Example: the reaction between ethene and hydrogen in the presence of a nickel catalyst. 1. Adsorption and activation of the reactants. 2. Migration of the adsorbed reactants on the surface.

Heterogeneous Catalysis


Example: the reaction between ethene and hydrogen in the presence of a nickel catalyst.

 

3. Reaction of the adsorbed substances. 4. Desorption (break away) of the products

II. Chemical Equilibrium a dynamic state where the concentrations of all reactants & products remain constant


Recall: Equilibrium state & vapor pressure, rate of evaporation = rate of condensation
 

A. Rxn. rates forward rate = reverse rate

NOT a condition in which products & reactants are in equal amts NOT a static condition

Reversible Reactions


Some reactions do not go to completion as we have assumed



They may be reversible a reaction in which the conversion of reactants to products and the conversion of products to reactants occur simultaneously

 

Forward: 2SO2(g) + O2(g) Reverse: 2SO2(g) + O2(g)

2SO3(g) 2SO3(g)

Reversible Reactions


The two equations can be combined into one, by using a double arrow, which tells us that it is a reversible reaction: 2SO2(g) + O2(g) 2SO3(g) A chemical equilibrium occurs, and no net change occurs in the actual amounts of the components of the system.

Reversible Reactions


Even though the rates of the forward and reverse are equal, the concentrations of components on both sides may not be equal


An equlibrium position may be shown:

A
1%
 

B
99%

or

A
99%

B
1%

Note the emphasis of the arrows direction It depends on which side is favored; almost all reactions are reversible to some extent

B. Equilibrium Constant:

Keq

Chemists generally express the position of equilibrium in terms of numerical values, not just percent

1. Relate values to the amounts (Molarity) of reactants & products at equilibrium

Equilibrium Constants
Consider this reaction:
The capital letters are the chemical, and the lower case letters are the balancing coefficient:

aA + bB


cC + dD

The equilibrium constant (Keq) is the ratio of product concentration to the reactant concentration at equilibrium, with each concentration raised to a power (which is the balancing coefficient).

aA + bB

cC + dD
Note that Keq has no units on the answer; it is only a number because it is a ratio

2. The equilibrium constant expression has this general form:

[C]c

[D]d

Keq = [A]a x [B]b

(brackets: [ ] = molarity concentration)

3. Equilibrium constants tells us whether products or reactants are favored:

if Keq > 1, products favored at equilibrium if Keq < 1, reactants favored

Write the equilibrium constant for the following problems:

1. CH3OH (g) 2. H2 (g) + I2 (g)



CH2O (g) + H2 (g) 2HI (g)

ANSWERS:

1.

[CH2O] x [H2 ] [CH3OH] Keq = [HI]2 Keq = [H2] x [I2]

2.

- Page 557

Does this favor the reactants or products?

Calculating Equilibrium


Calculate the equilibrium constant for the following reaction. 3H2(g) + N2(g) 2NH3(g) if at 25C there 0.15 mol of N2, 0.25 mol of NH3, and 0.10 mol of H2 in a 1.0 L container. Keq = [NH3]2 [H2]3 [N2] = [0.10 mol/L H2]3 [0.15 mol/L N2] [0.25 mol/L NH3]2 = 416.67 L2/mol2 = 420 L2/mol2

For the following reaction, calculate the value of the equilibrium constant:

2NB3 (g)

N2 (g) + 3Br2 (g)

[NBr3] = 2.07 x 10-3 M [N2] = 4.11 x 10-2 M [Br2] = 1.06 x 10-3 M



ANSWER:

Keq =

[N2] x [Br2]3 [NBr3]2

= 1.14 x 10-5

III. Applications A. Le Chateliers Principle if stress is applied to a system in equilibrium, the system changes in a way that relieves the stress (p. 598)


The French chemist Henri Le Chatelier (1850-1936) studied how the equilibrium position shifts as a result of changing conditions What items did he consider to be stress on the equilibrium? 1) Concentration Each of these will be 2) Temperature discussed in detail 3) Pressure

Le Chatelier Translated:


When you take something away from a system at equilibrium, the system shifts in such a away. way as to replace what youve taken away.

When you add something to a system at equilibrium, the system shifts in such a way added. as to use up what youve added.

1. Concentration adding more reactant produces more product, & removing the product as it forms will produce more product

Changing Concentration


If you add reactants (or increase their concentration), the forward reaction will speed up.
 More

product will form.  Equilibrium Shifts to the right



If you add products (or increase their concentration), the reverse reaction will speed up.
 More

reactant will form.  Equilibrium Shifts to the left

a. When a reactant or product is added to a system at equilibrium, the system shifts away from the added component

If you remove reactants (or decrease their concentration), the reverse reaction will speed up
 More

Changing Concentration

reactant will form.  Equilibrium Shifts to the left.



If you remove products (or decrease their concentration), the forward reaction will speed up
 More

product will form.  Equilibrium Shifts to the right

b. When a reactant or product is removed from a system at equilibrium, the system shifts towards the removed component

LeChatelier Example #1
A closed container of N2O4 and NO2 at equilibrium. NO2 is added to the container. N2O4 (g) + Energy 2 NO2 (g)

The equilibrium of the system shifts to left the _______ to use up the added NO2.

2. Temperature increasing the temp. causes the equilibrium position to shift in the direction that absorbs heat
If heat is one of the products (just like a chemical), it is part of the equilibrium so cooling an exothermic reaction will produce more product, and heating it would shift the reaction to the reactant side of the equilibrium:

C + O2(g)

CO2(g) + 393.5 kJ

Changing Temperature Page 600



As you raise the temperature the reaction proceeds in the endothermic direction. (Adding energy shifts the equilibrium so energy is absorbed.)
 Input  Too  The

heat, the reaction needs to cool itself down again.

cool down it needs to absorb the extra heat; the back reaction (endothermic) absorbs heat! position of equilibrium moves to the left and the new equilibrium mixture contains more A and B (less C and D)

a. Use heat as reactant or product to interpret shift of position i. Increase temp. shifts away from energy ii. Decrease temp. shifts towards energy

A + 2B

C + D

+ Energy

LeChatelier Example #2
A closed container of ice and water at equilibrium. The temperature is raised.

Ice + Energy

Water

The equilibrium of the system shifts to right the _______ to use up the added energy.

LeChatelier Example #3
A closed container of water and its vapor at equilibrium. Vapor is removed from the system. water + Energy vapor

The equilibrium of the system shifts to right the _______ to replace the vapor.

3. Pressure changes in P will only effect gaseous equilibria a. Increasing the pressure will usually favor the direction that has fewer molecules

N2(g) + 3H2(g)

2NH3(g)

For every two molecules of ammonia made, four molecules of reactant are used up this equilibrium shifts to the right with an increase in pressure

(a) A mixture of NH3(g), N2(g), and H2(g) at equilibrium. (b) The volume is suddenly decreased. (c) The new equilibrium position.

Changes in Pressure
 As

the pressure increases the reaction will shift in the direction of the least moles gases. high pressure 2H2(g) + O2(g) low pressure 2H2(g) + O2(g) 2 H2O(g) 2 H2O(g)

 At  At

LeChatelier Example #4
A closed container of N2O4 and NO2 at equilibrium. The pressure is increased. increased. N2O4 (g) + Energy 2 NO2 (g)

The equilibrium of the system shifts to left the _______ to lower the pressure, because there are fewer moles of gas on that side of the equation.

B. Solubility Equilibria
 

Ionic compounds (aka salts) differ in their solubilities Most insoluble salts will actually dissolve to some extent in water (slightly soluble)

The equilibria that we have considered thus far have been homogeneous (all the species are in the same phase, i.e. gas) 1. dissolution or precipitation of ionic compounds 2. heterogeneous

Solubility Product Constant

 

Consider: AgCl(s)

H2O

Ag+(aq) + Cl-(aq)

The equilibrium expression is:

Keq =

+] Ag

x[ [ AgCl ]

-] Cl

What was the physical state of the AgCl?

 

AgCl existed as a solid material, and is not in a solution = a constant concentration! the [ AgCl ] is constant as long as some undissolved solid is present (same with any pure liquid- do not change their conc.)

3. solubility product constant =

Ksp

4. pure solid or pure liquid is not included in the equilibrium expression From our example:

[Ag1+] x [Cl1-] Ksp =

Values of solubility product constants are given for some common slightly soluble salts

Ksp = [Ag1+] x [Cl1-]  Ksp = 1.8 x 10-10



5. The smaller the numerical value of Ksp, the lower the solubility of the compound  AgCl is usually considered insoluble because of its low value

To solve problems:
a) write the balanced equation, which splits the chemical into its ions b) write the equilibrium expression, and c) fill in the values known; calculate answer

Do not ever include pure liquids nor solids in the expression, since their concentrations cannot change (they are constant) just leave them out! Do not include the following in an equilibrium expression:  any substance with a (l) after it such as:

Br2(l), Hg(l), H2O(l), or CH3OH(l)



any substance which is a solid (s) such as:

Zn(s), CaCO3(s), or H2O(s)

ALWAYS include those substances which can CHANGE concentrations, which are gases and solutions:
 O2(g)

and NaCl(aq)

A saturated solution of a slightly soluble salt in contact with undissolved salt involves an equilibrium like the one below. CaF2 (s) <==> Ca2+ (aq) + 2F- (aq) Write the solubility product constant for this heterogeneous equilibria.

Ksp = [Ca2+][F-]2

Solid copper(II) chromate dissolves in water to give a solution that contains 1.1 x 10-5 g copper(II) chromate per liter at 23C. Calculate Ksp for solid copper(II) chromate at the temperature.

CuCrO4 (s) <==>

1.1 x 10-5 g CuCrO4

Cu2+ (aq) + CrO42- (aq)

= 7.0 x 10-8 mol CuCrO4

1 mole CuCrO4 156.07 g CuCrO4

Ksp = [Cu2+][CrO42-] = (7.0 X 10-8)(7.0 X 10-8) = 4.9 10-15

C. Common Ion Effect A common ion is an ion that is found in both salts in a solution
  

example: You have a solution of lead (II) chromate. You now add some lead (II) nitrate to the solution. The lead is a common ion This causes a shift in equilibrium (due to Le Chateliers principle regarding concentration), and is called the common ion effect

1. solubility product constant (Ksp) can also be used to predict whether a precipitate will form or not: a. if the calculated ion-product conc. is greater than the accepted value for Ksp, then a precipitate will form