CHEMICAL KINETICS AND EQUILIBRIUM

Lecture 2

Mag.chem., researcher Lauma Buša

 Contents of the lecture
• Reaction rate, change of rate with time
• Instantaneous rate
• First-order and second-order reactions
• Factors that affect reaction rates
• Physical and chemical equilibria
• Equilibrium constant
• Homogenous and heterogeneous equilibria
• Le Châtelier’s principle

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Why do some
chemical reactions
happen faster than
others?

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 Chemical kinetics

A branch of chemistry that

researches reaction rates
and their dependence from
various factors.

It is possible to describe
reaction mechanism by
using information about
reaction rate.
Chemistry, the Molecular Nature of Matter and Change, 7th ed.

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 Reaction rate
Overall: speed describes a change of the object (measurable value) over period of time.

Rate of chemical reaction: changes in reactant

or product concentrations over period of time

A rate of chemical reaction ∆𝒄

𝒗= ± 𝑚𝑜𝑙/𝐿 ∙ 𝑠
always has positive value!
∆𝒕

Reaction 𝒄𝑨,𝒂𝒕 𝒕𝒊𝒎𝒆 𝒕𝟐 − 𝒄𝑨,𝒂𝒕 𝒕𝒊𝒎𝒆 𝒕𝟏 ∆𝑨

𝒗=|− |=|− |
𝐴→𝐵 𝒕𝟐 − 𝒕 𝟏 ∆𝒕

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 Changes in concentrations of reactants and products

A→B
Products (B)
Reaction:

Reactant (A) concentration decreases ↓

Reactants (A)
Product (B) concentration increases ↑

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 Reaction rate change over time
As the reaction progresses, the rate of
reaction gradually decreases along with
reactant concentrations. The concentrations
of products are increasing.

Change of reaction rate IS NOT linear

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 Reaction instantaneous rate

Instantaneous rate is a rate at specific time of

the reaction (t).

Geometrically the instantaneous rate is represented by

c, mol/L

drawing a tangent for the point t. The rate is calculated:

∆𝑐 𝑐2 − 𝑐1
𝑣= =
∆𝑡 𝑡2 − 𝑡1

The instantaneous rate is equal to limit of the ratio of

concentration change against time interval when the time interval
Δt approaches zero.
t, s

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 2NO2 (g) → 2NO (g) + O2 (g) 300 °C

NO2 Concentration, mol/L

t, s
NO2 NO O2

0 0.0100 0 0
50 0.0079 0.0021 0.0011
100 0.0065 0.0035 0.0018

NO 150 0.0055 0.0045 0.0023

200 0.0048 0.0052 0.0026
250 0.0043 0.0057 0.0029

O2 300 0.0038 0.0062 0.0031

350 0.0034 0.0066 0.0033
400 0.0031 0.0069 0.0035
Chemical Priciples, 8th ed.

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Average rate of reaction for the time interval 50-100 s (NO2 decomposition):
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙
𝑐𝑁𝑂2,𝑡100𝑠 − 𝑐𝑁𝑂2,𝑡50𝑠 0.0065 𝐿 − 0.0079 𝐿 −0.0014
𝐿 mol
𝑣𝑎𝑣 = = = = −0.000028
𝑡100𝑠 − 𝑡50𝑠 100𝑠 − 50𝑠 50𝑠 L∙s

What is wrong
with the
obtained
result? ∆ 𝑁𝑂2 𝑚𝑜𝑙 −5
𝑚𝑜𝑙
𝑣𝑎𝑣 =− = − −0.000028 = 2.8 ∙ 10
∆𝑡 𝐿∙𝑠 𝐿∙𝑠

NO2 average decomposition rate, dependent on time (mol/L·s)

Time interval 0 → 50 50 → 100 100 → 150 150 → 200 200 → 250
∆ 𝑁𝑂2
− 4.2·10-5 2.8·10-5 2.0·10-5 1.4·10-5 1.0·10-5
∆𝑡

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 NO2 decomposition instantaneous speed at t = 100s:

𝑚𝑜𝑙
−0.0026
0,0075
𝑣𝑖𝑛𝑠𝑡 = − 𝐿 =
110𝑠
Concentration, mol/L

𝑚𝑜𝑙 𝑚𝑜𝑙
0.005 − 0.0076
=− 𝐿 𝐿 =
160𝑠 − 50𝑠

−5
𝑚𝑜𝑙
= 2.4 ∙ 10
𝐿∙𝑠
0,005

Chemical Priciples, 8th ed.50 Time, s 150

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 Reaction initial rate (t = 0s)

The calculations are the same as in case of

instantaneous rate, in this case a tangent to
the initial point of the reaction is being drawn.
c, mol/L

c2 − 𝑐1
𝑣𝑖𝑛𝑖𝑡 =
𝑡2 − 𝑡1

t, s

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 Reaction rates and stoichiometry
2NO2 (g) → 2NO (g) + O2 (g) 300 °C
NO2

Is 𝑣𝑁𝑂2 = 𝑣𝑁𝑂 = 𝑣𝑂2 ?

For a general reaction: aA + bB → cC + dD

NO

1 ∆𝐴 1 ∆𝐵 1 ∆𝐶 1 ∆[𝐷]
O2 𝑣=− ∙ =− ∙ = ∙ = ∙
𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡

Chemical Priciples, 8th ed.

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 Reaction rate law

Every chemical reaction is reversible: 2NO2 (g) ↔ 2NO (g) + O2 (g)

At the beginning of a reaction the rate depends only on the concentrations of

reactants. Therefore reaction rates usually are studied right after the start of
reaction.
For a general reaction: A → B 𝑣=𝑘 𝐴 𝑛
k – reaction rate constant, s-1
[A] – reactant concentration, mol/L
n – reaction order

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 Reaction rate constant and reaction order
Reaction order shows how the reaction rate depends on the concentrations of reactants.

First-order reactions: 𝑣 = 𝑘[𝐴] A→B

Rate
K units: 𝐬
−𝟏

Concentration

Second-order reactions: 𝑣 = 𝑘 𝐴 𝐵 𝑜𝑟 𝑣 = 𝑘 𝐴 2 A + B → C + D

𝑳
K units:

Rate
𝒎𝒐𝒍∙𝒔

Concentration

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 Reaction rate constant and reaction order

Zero-order reactions: 𝑣 = 𝑘 𝐴 0 = 𝑘 A→B

Rate
𝒎𝒐𝒍
K units:
𝑳∙𝒔
Concentrations

aA + bB + … → cC + dD + …
𝑣=𝑘 𝐴 𝑚 𝐵 𝑛…
Reaction order: z = m + n + …

Both reaction rate constant and reaction order are not to be calculated empirically.
The exact values can be detrmined only experimenatlly!

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 Various order reactions
• Zero-order reactions
Every radioactive decay:
14
6𝐶 → 14
7𝑁 + −10𝑒

• First-order reactions
Decomposition of nitrogen(V) oxide: 2N2O5(g) → 4NO2(g) + O2(g)

• Second-order reactions
Formation of hydrogen iodide: H2(g) + I2(g) → 2 HI(g)

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 Factors affecting reaction rate
• Concentration of reactants

As the concentration of reactants increases, the amount of

collisions increses and therefore also the reaction rate.

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 Factors affecting reaction rate
• Temperature

As the temperature rises,

the velocity of the particles
increases, and as a result,
the frequency and
strength of the collisions.

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 Factors affecting reaction rate
• Substances state of matter and the surface area
If the reactants are in the same state of matter and similar in
their physical properties, the reaction will be faster.

Pb(NO3)2 + 2KI → PbI2 + 2KNO3

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 Factors affecting reaction rate
• Substances state of matter and the surface area
With increase of the surface area the reaction rate
increases

t = 0s t = 10s t = 20s

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 Factors affecting reaction rate
• Pressure
As pressure increases, the distances between the particulates
decrease and the frequency of collisions increases.

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 Factors affecting reaction rate
• Presence of catalyst
Catalyst – a substance that accelerates the a chemical reaction
but remains in its initial amount and does not chemically change
2H2O2 (aq) → 2H2O (l) + O2↑ (g)

2Br- (aq) + H2O2 (aq) + 2H+ (aq) →

→ Br2 (aq) + 2H2O (l)

Br2 (aq) + H2O2 (aq) →

→ 2Br- (aq) + 2H+ (aq) + O2↑ (g)

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 Principle of catalyst
Any reaction can occur only if its reactants are able to overcome a specific
energy barrier called activation energy.

By adding a catalyst to the

reactants, the activation energy
of the reaction is decreased and
the reaction will happen faster.

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 Homogenous and heterogenous catalysis

Homogenous catalysis: reactants and catalyst are in the same

state of matter

The effect of freons on the ozone layer depletion

λ
CCl2F2(g) → CClF2(g) + Cl(g)

Heterogenous catalysis: reactants and catalyst are in different

states of matter

Decomposition of car
exhaust gases

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 Catalysts in biological systems
Enzymes or ferments – biological catalysts

Usually large molecules of complex size and structure. Designed to be able to catalyze one
particular type of reaction.

In one organism there are many thousands of ferments.

Reactions catalyzed by enzymes – homogenous catalysis in aqueous solutions

Ribbon diagram of human glyoxalase

This enzyme helps to decompose the

cancerogenous methyl glioxale formed
in various processes in the body
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EQUILIBRIUM PROCESSES
 Chemical and physical equilibrium
Equilibrium – a state of system whan all of its components are immobile in the reference system used

Physical equilibrium: the Chemical equilibrium: the reaction

physical processes in the system occurring in the system is reversible. At
are in equilibrium (evaporation, equilibrium state, the formation of
condensation, temperature products and their decomposition into
change, etc.) reactants are in balance.

N2O4 (g) ↔ 2NO2 (g)

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 Equilibrium of a chemical reaction
Let’s take a look at the reaction N2O4 (g) ↔ 2NO2 (g)

Forward reaction: N2O4 (g) → 2NO2 (g) 𝑣𝑓𝑜𝑟𝑤. = 𝑘𝑓𝑜𝑟𝑤 𝑁2 𝑂4

Reaction rate is being described: 2
Backward reaction: 2NO2 (g) → N2O4 (g) 𝑣𝑏𝑎𝑐𝑘𝑤. = 𝑘𝑏𝑎𝑐𝑘𝑤 𝑁𝑂2

Initially, nitrogen dioxide forms from nitrogen tetroxide. After an increase in NO2 concentration, also the backward
reaction begins and the reactants - N2O4 - are formed again. The equilibrium is reached when forward and backward
reaction rates become the same and the concentrations of reactants and products remain unchanged.

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 Equilibrium constant

aA + bB ↔ cC + dD
𝒄
𝑪 𝑫𝒅 Kc – reaction equilibrium constant

𝑲𝒄 = 𝒂
[C] – molar concentration of product C, mol/L
𝑨 𝑩𝒃 C
– coefficient in the chemical reaction before product C

𝑨 𝒂 𝑩𝒃 𝟏
Backward reactions cC + dD ↔ aA + bB equilibrium constant: 𝑲′𝒄 = = 𝒄
𝑪 𝒄 𝑫 𝒅 𝑲

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 Calculation of equilibrium constant
2
𝑚𝑜𝑙
N2(g) + 3H2(g) ⇄ 2NH3(g) 𝑁𝐻3 2 3.1 ∙ 10−2 𝐿
𝐾𝑐 = = 3 =
[𝑁2 ] 𝐻2 3 𝑚𝑜𝑙 𝑚𝑜𝑙
8.5 ∙ 10−2 𝐿 3.1 ∙ 10−3 𝐿
The equilibrium concentrations have been
determined for the reaction at 127 °C:
𝑚𝑜𝑙 2
9.6 ∙ 10−4 2
𝐿
= =
[NH3] = 3.1·10-2 mol/L −2 𝑚𝑜𝑙 −8 𝑚𝑜𝑙 3
8.5 ∙ 10 3 ∙ 10
𝐿 𝐿3
[N2] = 8.5·10-1 mol/L
[H2] = 3.1·10-3 mol/L 2
𝑚𝑜𝑙
9.6 ∙ 10−4 2 𝐿2
𝐿
= 4 = 3.8 ∙ 105
𝑚𝑜𝑙 𝑚𝑜𝑙 2
2.5 ∙ 10−9 4
𝐿

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 Relationships between different equilibrium constants

𝑪 𝒄 𝑫𝒅
aA + bB ⇄ cC + dD 𝑲𝒄 = 𝒂
𝑨 𝑩𝒃

𝑨 𝒂 𝑩𝒃 𝟏
cC + dD ⇄ aA + bB 𝑲′𝒄 = 𝒄 𝒅
= 𝒄
𝑪 𝑫 𝑲

𝑪 𝒏𝒄 𝑫 𝒏𝒅
naA + nbB ⇄ ncC + ndD ′′
𝑲𝒄 = 𝒏𝒂
= 𝑲 𝒏
𝒄
𝑨 𝑩 𝒏𝒃

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 Relationships between different equilibrium constants

𝑪 𝒄 𝑫𝒅
aA + bB ⇄ cC + dD 𝟏
𝑲𝒄 = 𝒂
𝑨 𝑩𝒃

𝑬 𝒆 𝑭𝒇
cC + dD ⇄ eE + fF 𝟐
𝑲𝒄 = 𝒄
𝑪 𝒅𝒅

𝑪 𝒄 𝑫𝒅 𝑬𝒆𝑭 𝒇 𝑬𝒆𝑭𝒇
aA + bB ⇄ eE + fF 𝑲𝒄 = 𝒂 𝒃
∙ = = 𝑲 𝟏 ∙ 𝑲𝟐
𝒄 𝒄
𝑨 𝑩 𝑪𝒄𝑫 𝒅 𝑨𝒂𝑩𝒃

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 Magnitude of equilibrium constant
If forward reaction dominates at the equilibrium state: Kc > 1

If backward reaction dominates at the equilibrium state : Kc < 1

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 Homogenous equilibrium
All the substances in the reaction are in the same state of matter
If all substances are in gaseous phase Kc (concentration constant) or Kp (partial pressure constant) can be used.

2NO(g) + O2(g) ⇄ 2NO2(g)

2
𝑁𝑂2 2 Partial pressure: part of the total pressure produced 𝑝𝑁𝑂2
𝐾𝑐 = 𝐾𝑝 = 2
𝑁𝑂 2 [𝑂2 ] by one of the gases in the gas mixture.
𝑝𝑁𝑂 ∙ 𝑝𝑂2

Kc ≠ Kp

𝐾𝑝 = 𝐾𝑐 𝑅 ∙ 𝑇 ∆𝑛𝑔
= 𝐾𝑐 0.08206 ∙ 𝑇 ∆𝑛𝑔 , where T – temperature, K
Δng – the difference between the number of
gaseous molecules (products-reactants)
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 Heterogeneous equilibrium
Substances in the reaction are in different states of matter.
CaCO3(s) ⇄ CaO(s) + CO2(g)

Equilibrium constant can be written: 𝐾𝑐 = [CO2 ] or 𝐾𝑝 = pCO2

When writing the equilibrium constant

equation for heterogeneous equilibrium, it
does NOT contain pure solids and pure
liquid substances!

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 Concentrations of substances at equilibrium
If the chemical reaction equilibrium constant and the initial concentrations of reactants are known, the
concentrations of the reactants and products at the equilibrium can be calculated

H2(g) + I2(g) ⇄ 2HI(g) Kc=50.5

H2 I2 HI
Initial concentration (mol/L) 1.00 2.00 0
Change of concentration (mol/L) -x -x +2x
Equilibrium concentration (mol/L) 1.00-x 2.00-x 2x

𝐻𝐼 2 2𝑥 2 4𝑥 2
𝐾𝑐 = = = = 50,5 4𝑥 2 = 50.5(𝑥 2 − 3𝑥 + 2) 46.5𝑥 2 − 151.5𝑥 + 101 = 0
𝐻2 [𝐼2 ] (1.00 − 𝑥)(2.00 − 𝑥) 2 − 3𝑥 + 𝑥 2
Equilibrium concentrations:
−(−151.5) ± 151.52 − 4 ∙ 46.5 ∙ 101 𝑥1 = 2.32
𝑥1,2 = 𝒙𝟐 = 𝟎. 𝟗𝟒
2 ∙ 46.5 [H2]=0.06M; [I2]=1.06M; [HI]=1.88M
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 Le Châtelier’s principle
When any system at equilibrium is subjected to change in concentration, temperature, volume, or pressure,
then the system readjusts itself to counteract (partially) the effect of the applied change and a new equilibrium
is established. Effect of pressure change

Effect of concentration change Pressure changes only affect reactions involving

By increasing the concentration of one of the
substances, the balance moves towards the
direction in which the substance is used.
gaseous substances. As pressure increases, the
balance moves in the direction in which the number
of gaseous molecules is lower. As pressure
decreases, the balance moves in the direction in
which the number of gaseous molecules is higher.

Effect of a catalyst
Effect of temperature change
The addition of a catalyst does not affect the
equilibrium, it only accelerates the reaction speed As the temperature rises, the balance moves
- the equilibrium is reached faster. towards the endothermic reaction, but, lowering
the temperature, towards the exothermic reaction.
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