1 SUMMARY

p. 185 – 204

Energy Changes in Chemical Reactions

Rates of Chemical Reactions

ENERGY CHANGES IN CHEMICAL REACTIONS

 For a reaction to take place, bonds have to be broken and new bonds have to form. E.g. in the
reaction A2 + B2  2AB the bonds in A2 and B2 have to be broken and the new bonds in AB
have to form.
 To break the bonds in A2 and B2, energy is needed.
 To form the new bonds in AB, energy is released.

A2 B2 +EA –E 2AB
reactants activated complex products

 Activation energy (EA or Ea) = the minimum energy needed for a reaction to take place.

 An Activated complex is the unstable transition state from reactants to products.

 All substances have a energy quantity which is called enthalpy (H). During a chemical reaction
the enthalpy changes. The change in enthalpy is called the heat of reaction (ΔH):
ΔH = Hproducts – Hreactants

 Heat of reaction (ΔH) = the energy absorbed or released in a chemical reaction.

 An Exothermic reaction is a reaction in which energy is released

 An Endothermic reaction is a reaction in which energy is absorbed.

EXOTHERMIC REACTION ENDOTHERMIC REACTION

Potential energy
Potential energy

E2 E2

E3
E1
H < 0 H > 0
E3 E1

For the reaction A2 + B2  2AB For the reaction A2 + B2  2AB

E1 = energy of reactants (A2 + B2) E1 = energy of reactants (A2 + B2)

E2 = energy of activated complex E2 = energy of activated complex
E3 = energy of products (2AB) E3 = energy of products (2AB)
E2 – E1 = activation energy = EA E2 – E1 = activation energy = EA

H H = Eproducts
= Hproducts – Ereactants
– Hreactants H = Hproducts – Hreactants
 = E3 – E1 = E3 – E1 = E3 – E1
< 0 (negative)
< 0 (negative) > 0 (positive)


In the graphs above:

 A positive catalyst is a substance that increases the rate of a
chemical reaction without itself undergoing a permanent change. without catalyst
with catalyst

 A positive catalyst functions by reacting with the reactants in such a way that the reaction takes an
 alternative route
 of lower activation energy.

 A positive catalyst increases reaction rate, a negative catalyst decreases reaction rate.
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THE COLLISION THEORY

1. For a reaction between 2 particles of the reactants to take place:
1.1. the particles have to collide; and
1.2. the collision has to be effective.

2. For an effective collision between particles:

2.1. the particles have to be correctly orientated; and
2.2. the kinetic energy of the particles (Ek) has to be greater or equal to the activation energy
(EA) of the reaction  Ek (of particles)  EA (of reaction).

REACTION RATE

 The rate of a reaction (reaction rate) = the change in concentration of reactants or products per
time unit.

Rate = -3 -1
Unit is mol∙dm ∙s
–1 –1 –3 –1
 Examples of other units for reaction rate: mol.s ; g·min , mol·dm ·s , etc.

FACTORS THAT INFLUENCE THE RATE OF REACTIONS

1 Nature of the reactants  Reactants in gas form as higher rate than solids.
 Ions in solution has higher rate than ionic solids.
 Smaller molecules has higher rate than bigger ones (e.g.
combustion of methane is quicker than that of octane).
2 Concentration* of reactants Increases the number of The higher the concentration,
particles that can collide the higher the rate
effectively
3 Temperature of reactants Increase the Ek of colliding The higher the temperature,
particles the higher the rate
4 Presence of a catalyst Decreases the Ea of the The rate increases in the
reaction. presence of a +catalyst
5 Surface area of reactants Increases the number of The greater the surface area,
particles that can collide the higher the rate
effectively

 * Concentration is mole per volume ( c = ).

 Increase concentration of solutions by greater mass of solute, or smaller volume of solvent.
 Increase concentration of gases by decreasing volume, ∴ greater pressure on gas.

 It can be determined from the nature of the reactants what can be done to increase the reaction
rate:
 for a reactant in solution: → increase the concentration of the solution;
→ increase the temperature of the solution.
 for a solid reactant: → use in powdered form.
 for a gas: → increase the concentration of the gas;
→ increase the temperature of the gas.

Zn(s) + 2HC (aq)  ZnC2(aq) + H2(g) H2 (g) + C2 (g) → 2HC (g)

use increase c increase c increase c

powder increase T increase T increase T

 In all cases a positive catalyst can be added.

MEASUREMENT OF REACTION RATE

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 For a reaction that liberates gas the rate of the reaction can be determined by measuring the rate
of gas liberation.

Zn(s) + 2HC(aq)  ZnC2(aq) + H2(g) CaCO3(s) + 2HC(aq)  CaC2(aq) + H2O() + CO2(g)

METHOD 1 METHOD 2

Close the reaction The reaction takes place in

container with a rubber an open container, on a
stopper and collect the scale. Measure the mass
gas in a syringe. Measure of the reaction mixture
the volume of gas that is regularly.
collected in the syringe
regularly.

The volume of gas that collects Rate of reaction = gradient The mass of the beaker and
in the syringe increases. the contents decrease as the
gas escapes from the beaker.
 t1 rate is high;
slow  t2  rate is lower;

Mass of beaker
Volume gas

and contens
 t3  rate = 0
fast The reaction has stopped.
fast
time slow
t0 t1 t2 t3
t0 t1 t2 t3 time

is obtained when the rate

is increased:
Mass of beaker

 higher temperature;
and contents
Volume gas

 higher concentrations;
 use pulverized solids;
 add a catalyst.
time
is obtained when the rate time
is decreased.

 In a reaction where a precipitate forms, the rate of the reaction can be determined by the rate at
which the precipitate forms, e.g.:

Na2S2O3(aq) + 2HC  2NaC + H2O() + SO2(g) + S(s)

METHOD: Place the beaker in which the reaction takes place (and the precipitate forms) on a
piece of paper with a mark (e.g. a cross). Take the time it takes for the cross to “disappear”.

cross disappears
as precipitate forms

Graphs: Rate of reaction =

)
me
1
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Time

[Na2S2O3] or [HCl]

)
time
1
Time

Reaction rate (
Temperature
Temperature

EXPLANATION OF FACTORS IN TERMS OF COLLISION THEORY

 At a higher temperature the rate of a chemical reaction increases:

Explanation: At a higher temperature:
- the particles move faster;
- ∴ the particles have more Ek;
- ∴ more particles have Ek EA;
- ∴ more effective collisions per time unit;
- ∴ the rate of the reaction increases.

 At a higher concentration the rate of a chemical reaction increases:

Explanation: At a higher concentration:
- more particles are present;
- ∴ more collisions take place;
- ∴ more collisions take place between particles with Ek EA;
- ∴ more effective collisions per time unit;
- ∴ the rate of the reaction increases.

 With the addition of a catalyst the rate of a chemical reaction increases:

Explanation: With the addition of a catalyst:
- the activation energy (EA) of the reaction decreases;
- ∴ more particles have Ek EA;
- ∴ more effective collisions per time unit;
- ∴ the rate of the reaction increases.

 With the powdering of a solid reactant, the rate of a chemical reaction increases:
Explanation: With the powdering of a solid reactant:
- the contact area of the solid reactant increases;
- ∴ more collisions takes place;
- ∴ more collisions take place between particles with Ek EA;
- ∴ more effective collisions per time unit;
- ∴ the rate of the reaction increases.

MAXWELL-BOLTZMANN GRAPHS
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 Ek  T: The average kinetic energy of the particles in a substance is directly proportional to the
temperature or the substance, ∴ the higher the temperature, the greater the average kinetic
energy of the particles.

 A Maxwell-Boltzmann graph shows the distribution of kinetic energy of the particles in a system.

Fraction of
particles with Fraction of particles
given Ek with Ek = EA

Particles with
enough Ek for a reaction
Ek  EA

0
EA Kinetic energy

 The curve is drawn through the origin, because no particles have EK = 0 J.

 The area under the graph = the total number of particles in the system.
 The peak of the curve = the average EK of the particles. That is the most probable EK of the
particles.
 The shaded area represents the fraction of particles which has kinetic energy equal or greater
than the activation energy (∴ Ek EA). This fraction of particles can therefore perform effective
collisions if the orientation is correct, since they have enough kinetic energy.

At a higher temperature the curve changes:

 The average EK of the particles increases as the

temperature increases ∴ the peak is more to the right.
 The number of particles remains the same,
∴ the area under the graph remains the same.
 ∴ the peak is lower and broader.
Fraction of particles

Low Temp
with given Ek

High Temp

EK of particles
EA

 At a higher temperature the rate of a chemical reaction increases:

Explanation: At a higher temperature:
- the particles move faster;
- ∴ the particles have more Ek;
- ∴ more particles have Ek EA;
- ∴ more effective collisions per time unit;
- ∴ the rate of the reaction increases.

∴ the area under the graph to the right of the EA-broken line increases.

At a higher concentration the curve changes:

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 The number of particles increases,

∴ the area under the graph increases.
 The peak is higher, but at the same place.
Fraction of particles

low concentration
with given Ek

high concentration

EK of particles
EA

 At a higher concentration the rate of a chemical reaction increases:

Explanation: At a higher concentration:
- more particles are present;
- ∴ more collisions take place;
- ∴ more collisions take place between particles with Ek EA;
- ∴ more effective collisions per time unit;
- ∴ the rate of the reaction increases.

∴ the area under the graph to the right of the EA-broken line increases.

With the addition of a catalyst:

 The curve does not shift.

 EA of the reaction now has a lower value.
Fraction of particles
with given Ek

EA with catalyst

EA without catalyst

EK of particles

 With the addition of a catalyst the rate of a chemical reaction increases:

Explanation: With the addition of a catalyst:
- the activation energy (EA) of the reaction decreases;
- ∴ more particles have Ek EA;
- ∴ more effective collisions per time unit;
- ∴ the rate of the reaction increases;

∴ the area under the graph to the right of the EA-broken line increases.

With the powdering of a solid reactant:

 This factor does NOT show on the Maxwell-Boltzmann graphs.