Chemical kinetics

Lecture III

CHAPTER 14

Tamriko Supatashvili
2019
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What does rate of reaction mean?
The speed of different chemical reactions varies hugely. Some reactions
are very fast and others are very slow.
The speed of a reaction is called the rate of the reaction.

What is the rate of these reactions?

rusting baking explosion

slow fast very fast

 the rate of a reaction
• The rate of a reaction measures how fast a
reactant is consumed or how fast a product is
formed.
The rate is expressed as a ratio of the change in
concentration to elapsed time.
We know that any reaction can be represented by the
general equation
Reactants → products

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 the rate of a reaction

• in which Δ[A] and Δ[B] are the changes in

concentration (in molarity) over a period

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 The rate of reaction A → B, represented as the decrease of A
molecules with time and as the increase of B molecules with
time.

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 Changing the rate of reactions
What factors affect the rate of reactions?

Anything that increases the number of successful collisions between reactant

particles will speed up a reaction.
 increased temperature

 increased concentration of dissolved

reactants, and increased pressure of gaseous
reactants

 increased surface area of solid reactants

 use of a catalyst.
 Slower and slower!
Reactions do not proceed at a steady rate. They start off at a certain speed, then
get slower and slower until they stop.
As the reaction progresses, the concentration of reactants decreases.

This reduces the frequency of collisions between particles and so the

reaction slows down.

0% 25% 50% 75% 100%

reactants
percentage completion of reaction
product
 How can rate of reaction be
measured?
Measuring the rate of a reaction means measuring the change in the amount
of a reactant or the amount of a product.

What can be measured to calculate the rate of reaction between

magnesium and hydrochloric acid?

hydrochloric magnesium
magnesium + acid  chloride + hydrogen

 The amount of hydrochloric acid used up (cm3/min).

 The amount of magnesium chloride produced (g/min).
 The amount of hydrogen product (cm3/min).
 Setting up rate experiments
What equipment is needed to investigate the rate of hydrogen
production?
glass tube rubber connecter gas syringe

conical rubber bung

flask

hydrochloric
acid

magnesium
 Calculating rate of reaction from
How can the rate of reaction be calculated from a graph?
graphs
70
hydrogen produced (cm3)

60
50 x
rate of reaction = y
40
x
30
20 y
10
0
0 10 20 30 40 50
time (seconds)

The gradient of the graph is equal to the initial rate of reaction at that time

rate of reaction = 45 cm3 rate of reaction = 2.25 cm3/s

20 s
activation energy and temperature dependence
of rate constants
• the activation energy (Ea), which is the minimum
amount of energy required to initiate a chemical
reaction

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 Effect of temperature on rate
The higher the temperature, the faster the rate of a reaction. In many reactions,
a rise in temperature of 10 °C causes the rate of reaction to approximately
double.
Why does increased temperature increase the
rate of reaction?

At a higher temperature, particles have more

energy. This means they move faster and are
more likely to collide with other particles.

When the particles collide, they do so with

more energy, and so the number of
successful collisions increases.
Temperature and particle collisions
 Temperature and batteries
Why are batteries more likely to rundown more quickly in cold weather?

At low temperatures the reaction that

generates the electric current
proceeds more slowly than at higher
temperatures.

This means batteries are less likely to

deliver enough current to meet
demand.
 How does temperature affect rate?
The reaction between sodium thiosulfate and hydrochloric acid produces sulfur.

sodium hydrochloric sodium sulfur

thiosulfate + acid

chloride + dioxide + sulfur + water

Na2S2O3 2HCl 2NaCl SO2 S H2O

(aq)
+ (aq)

(aq) + (g)
+ (s) + (l)

Sulfur is solid and so it turns the solution cloudy.

How can this fact be used to measure the effect of temperature on

rate of reaction?
 Effect of concentration on rate of reaction
The higher the concentration of a dissolved reactant, the faster the rate of a
reaction.
Why does increased concentration increase the rate of reaction?

At a higher concentration, there are more particles in the same amount of

space. This means that the particles are more likely to collide and therefore
more likely to react.

lower concentration higher concentration

Concentration and particle collisions
 Effect of pressure on rate of reaction
Why does increasing the pressure of gaseous reactants increase the rate of
reaction?
As the pressure increases, the space in which the gas particles are
moving becomes smaller.

The gas particles become closer together, increasing the frequency of collisions.
This means that the particles are more likely to react.

lower pressure higher pressure

 Effect of surface area on rate of
reaction
Any reaction involving a solid can only take place at the surface of the
solid.
If the solid is split into several pieces, the surface area increases. What
effect will this have on rate of reaction?

low surface area high surface area

This means that there is an increased area for the reactant particles to collide
with.

The smaller the pieces, the larger the surface area. This means more
collisions and a greater chance of reaction.
Surface area and particle collisions
 Reaction between a carbonate and
acid
Marble chips are made of calcium carbonate. They react with hydrochloric acid
to produce carbon dioxide.

calcium hydrochloric  calcium carbon

carbonate + acid chloride + water + dioxide
CaCO3 2HCl CaCl2 H2O CO2
(aq) + (aq) 
(aq) + (aq) + (g)

The effect of increasing surface area on the rate of reaction can be measured by
comparing how quickly the mass of the reactants decreases using marble chips
of different sizes.
 • catalysis

A catalyst
is a substance that increases the rate of a reaction by lowering
the activation energy.

There are three general types of catalysis, depending on the

nature of the rate increasing substance:
• heterogeneous catalysis,
• homogeneous catalysis,
• enzyme catalysis.
 What are catalysts?
Catalysts are substances that change the rate of a reaction without being used
up in the reaction.

Catalysts never produce more product – they just produce the same
amount more quickly.

Ea without
Different catalysts work in different
catalyst
ways, but most lower the reaction’s
activation energy (Ea).
energy (kJ)

Ea with
catalyst

reaction (time)
 Everyday catalysts
Many catalysts are transition metals or their compounds. For example:

 Nickel is a catalyst in the production of margarine (hydrogenation

of vegetable oils).

 Iron is a catalyst in the production of ammonia from nitrogen and

hydrogen (the Haber process).

 Platinum is a catalyst in the catalytic

converters of car exhausts. It
catalyzes the conversion of carbon
monoxide and nitrogen oxide into the
less polluting carbon dioxide and
nitrogen.
 Catalysts in industry
Why are catalysts so important for industry?

 Products can be made more quickly,

saving time and money.

 Catalysts reduce the need for high

temperatures, saving fuel and reducing
pollution.

Catalysts are also essential for living cells. Biological catalysts are special
types of protein called enzymes.
 catalysis
• In heterogeneous catalysis, the reactants and
the catalyst are in different phases
• homogeneous catalysis the reactants and
catalyst are dispersed in a single phase, usually
liquid.
• Of all the intricate processes that have evolved
in living systems, none is more striking
or more essential than enzyme catalysis.
Enzymes are biological catalysts.

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chemical balance the concepts of equilibrium, ways of
expressing balance constants
• Chemical equilibrium describes the state in which the rates of
forward and reverse reactions are equal and the
concentrations of the reactants and products remain
unchanged with time.

K - equilibrium constant.

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• the rates of the forward and reverse reactions are equal and
• the concentrations of the reactants and products remain constant

Chemical equilibrium

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15.1
28
 N2O4 (g) 2NO2 (g)

equilibrium

equilibrium
equilibrium

Start with NO2 Start with N2O4 Start with NO2 & N2O4

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29
 constant
The NO2-N2O4 System at 25ºC

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30
 aA + bB cC + dD

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

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31
________________ _________________ applies to reactions in which all reacting
species are in the same phase.

N2O4 (g) 2NO2 (g)

Kc = Kp =

In most cases

Kc  K p

aA (g) + bB (g) cC (g) + dD (g)

Kp = Kc(RT)n

n = moles of gaseous products – moles of gaseous reactants

= (c + d) – (a + b)
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15.2
32
 Homogeneous Equilibria

we can write

in which PNO2 and PN2O4 are the equilibrium partial

pressures (in atmospheres) of NO2 and N2O4,
respectively

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 Heterogeneous Equilibria

Alternatively, we can express the equilibrium

constant as

The equilibrium constant in this case is numerically equal to

the pressure of CO2 gas, an easily measurable quantity.

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 Factors of chemical balance

• concentration,
• pressure,
• Volume,
• temperature.
Le Chatelier’s principle
if an external stress is applied to a system at
equilibrium, the system adjusts in such a way that
the stress is partially offset as it tries to
reestablish equilibrium.

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 Le Châtelier’s Principle
If an external stress is applied to a system at equilibrium, the system adjusts in such
a way that the stress is partially offset as the system reaches a new equilibrium
position.

Changes in Concentration

N2 (g) + 3H2 (g) 2NH3 (g)

Equilibrium shifts
_________ to Add
offset stress NH3

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36
 Le Châtelier’s Principle

• Changes in Concentration continued

Add

aA + bB cC + dD

Change Shifts the Equilibrium

Increase concentration of product(s)

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37
 Le Châtelier’s Principle

• Changes in Concentration continued

Remove

aA + bB cC + dD

Change Shifts the Equilibrium

Decrease concentration of product(s)

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38
 Le Châtelier’s Principle

• Changes in Concentration continued

Add

aA + bB cC + dD

Change Shifts the Equilibrium

Increase concentration of reactant(s)

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15.5
39
 Le Châtelier’s Principle

• Changes in Concentration continued

Remove

aA + bB cC + dD

Change Shifts the Equilibrium

Decrease concentration of reactant(s)

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15.5
40
 uncatalyzed catalyzed

Catalyst lowers Ea for ________ forward and reverse reactions.

Catalyst does not change __________ _______________

or _______________ _______________ .

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41
 Le Châtelier’s Principle

Change Equilibrium
Constant
Change Shift Equilibrium

Concentration

Pressure

Volume

Temperature

Catalyst

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42
Acids and Bases
Chapter 16
 Acids
Have a ___sour______ taste. Vinegar owes its taste to
acetic acid. Citrus fruits contain citric acid.

React with certain metals to produce ___hydrogen___________ gas.

React with carbonates and bicarbonates to produce __carbon dioxide_____

gas

Bases
Have a ____bitter______ taste.

Feel __slipery______________. Many soaps contain bases.

16.3
Arenius_________ acid is a substance that produces H+ (H3O+) in water

_____Arenius____ base is a substance that produces OH- in water

16.3
A _Brostoned- Lowry__ acid is a proton donor

A __ Brostoned- Lowry
base is a proton acceptor

base acid acid base

conjugate conjugate
base acid
acid base

16.1
 Lewis Theory
Acid is electron pair acceptor
Base is electron pair donor

NH3 + H+ = NH4+
NH3 is electorn pair donor
And H+ is electron pair acceptor

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 Acid-Base Properties of Water

H2O (l) H+ (aq) + OH- (aq)

__________________ of water

+ -
H O + H O
[ H O H
] + H O

H H H

conjugate
base
acid

H2O + H2O H3O+ + OH-

conjugate
acid
base

16.2
 The Ion Product of Water

Kc = [H+][OH-] [H2O] = constant

H2O (l) H+ (aq) + OH- (aq) [H2O]

Kc[H2O] = [H+][OH-]

Solution Is

[H+] = [OH-]

[H+] > [OH-]

[H+] < [OH-]

16.2
 pH – A Measure of Acidity

pH = -log [H+]

Solution Is At 250C

neutral [H+] = [OH-] [H+] = 1 x 10-7 pH =7

acidic [H+] > [OH-] [H+] > 1 x 10-7 pH < 7

basic [H+] < [OH-] [H+] < 1 x 10-7 pH >7

pH [H+] pH [H+]

16.3
pHs of some common fluids

pOH = -log [OH-]

[H+][OH-] =

-log [H+] – log [OH-] = ________

pH + pOH = 14

16.3
The pH of rainwater collected in a certain region of the northeastern United
States on a particular day was 4.82. What is the H+ ion concentration of the
rainwater?

pH = -log [H+]

-antilog (pH) = -antilog (-log [H+])

antilog -4.82 = [H+]

[H+] = 10-pH = 10-4.82 = _____________ M

16.3
Strong Electrolyte = __________________________
H2O
NaCl (s) Na+ (aq) + Cl- (aq)

Weak Electrolyte = __________________________

CH3COOH CH3COO- (aq) + H+ (aq)

Strong Acids are strong electrolytes

HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq)

HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)

HClO4 (aq) + H2O (l) H3O+ (aq) + ClO4- (aq)

H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq)

16.4
 Weak Acids are weak electrolytes

HF (aq) + H2O (l) H3O+ (aq) + F- (aq)

HNO2 (aq) + H2O (l) H3O+ (aq) + NO2- (aq)

HSO4- (aq) + H2O (l) H3O+ (aq) + SO42- (aq)

H2O (l) + H2O (l) H3O+ (aq) + OH- (aq)

Strong Bases are strong electrolytes

H2O
NaOH (s) Na+ (aq) + OH- (aq)
H2O
KOH (s) K+ (aq) + OH- (aq)
H2O
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)

16.4
Weak Bases are weak electrolytes

F- (aq) + H2O (l) OH- (aq) + HF (aq)

NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

Conjugate acid-base pairs:

• The conjugate base of a strong acid has no measurable strength.
• H3O+ is the strongest acid that can exist in aqueous solution.
• The OH- ion is the strongest base that can exist in aqueous
solution.

16.4
Relative Strengths of Conjugate Acid-Base Pairs

16.4
Strong Acid Weak Acid

16.4
 What is the pH of a 2 x 10-3 M HNO3 solution?

HNO3 is ___strong acid_______________________.

Start 0.002 M 0.0 M 0.0 M

HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)

End 0.0 M 0.002 M 0.002 M

pH = -log [H+] = -log [H3O+] = -log(0.002) = _______

16.4
What is the pH of a 1.8 x 10-2 M Ba(OH)2 solution?

Ba(OH)2 is a strong base – 100% dissociation.

Start 0.018 M 0.0 M 0.0 M

Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)

End 0.0 M 0.018 M 0.036 M

pH = 14.00 – pOH = 14.00 + log(0.036) = _______

16.4
Weak Acids (HA) and Acid Ionization Constants
HA (aq) + H2O (l) H3O+ (aq) + A- (aq)

HA (aq) H+ (aq) + A- (aq)

Ka =

Ka is the acid ionization constant

weak acid
Ka strength

16.5
percent ionization = Ionized acid concentration at equilibrium x 100%
Initial concentration of acid

For a monoprotic acid HA

[H+]
Percent ionization = x 100% [HA]0 = initial concentration
[HA]0

16.5
Weak Bases and Base Ionization Constants
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

Kb = [NH4+][OH-]
[NH3]

Kb is the base ionization constant

weak base
Kb strength

Solve weak base problems like weak acids except solve

for [OH-] instead of [H+].

16.6
 Glossary
activation energy – The amount of energy
needed to start a reaction.
catalyst – A substance that increases the rate of a
chemical reaction without being used up.
concentration – The number of molecules of a
substance in a given volume.
enzyme – A biological catalyst.
rate of reaction – The change in the
concentration over a certain period of time.

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