Chemical Reactions:

Chemical Thermodynamics
and Kinetics

JMBarcelo 2019
Thermodynamics

• Thermodynamics mean “flow of heat”

• Purposes:
• Predicts feasibility of a physical process or chemical reaction
• Predicts whether a chemical reaction would occur
spontaneously or not
• Helps to determine the extent to which a reaction would takes
place

HOWEVER!
• It does not say anything about the rate.
• It applies only to matter in bulk and not to individual atoms or
molecules.
System, Surroundings and Boundary

• System – three-dimensional region of physical space on which we

wish to focus our attention

• The rest of the physical universe constitutes the surroundings of

the system.

• The boundary is the closed three-dimensional surface that

encloses the system and separates it from the surroundings
• The boundary may (and usually does) coincide with real physical surfaces:
the interface between two phases, the inner or outer surface of the wall of a
flask or other vessel, and so on
Types of System

• Homogeneous system: Consists of only one phase and uniform

thought.
• Example: solution of sugar in water.

• Heterogeneous system: Consists of two or more phases and is

not uniform throughout
Example: ice in water, chloroform in water.
Types of System

• Open system: A system which can exchange both energy and

matter with the surroundings (e.g. beaker of water)

• Closed system: A system which can exchange energy but not

matter with the surroundings (e.g. water in as stoppered bottle)

• Isolated System: In system in which neither matter nor energy

can exchange with its surroundings
Thermodynamic Process

• “Process” - the method by which the state of a system is changed

• Isothermal process: Process carried out at constant temperature.

Exchange of heat takes place between system and surroundings
• dT = 0

• Adiabatic process: Process in which no exchange of heat takes

place. The temperature of the system may increase or decrease
during adiabatic process.
• dQ =0

• Isobaric process : Carried out at constant pressure

• Isochoric process: Carried out at constant volume

 First Law of Thermodynamics

∆U = q + w
Energy can be neither created nor destroyed, but it can be converted from
one form to another.

Internal Energy = heat added to the system and the work done by the system

• Heat - transfer of energy across the boundary caused by a

temperature gradient at the boundary.

• Work - transfer of energy across the boundary caused by the

displacement of a macroscopic portion of the system

• Note: In reality, heat and work are NOT mutually convertible to each
other
Second Law of Thermodynamics

The state of entropy of the entire universe, as an isolated system, will always
increase over time. all spontaneous processes produce an increase in the
entropy of the universe
 Second Law of Thermodynamics

Second law of thermodynamics predicts the direction of heat flow.

It explains the reason for why complete conversion of energy into work is
not possible.

It predicts the feasibility of a process.

It introduces two new thermodynamic functions entropy and free energy

to explain spontaneity.
Conditions for Spontaniety
 Thermodynamic Concepts (Activity 8b)

∆Go
• change in the standard Gibbs free energy for a process
• ∆Go = Go(products) – Go(reactants)
• Unit: J/mol or kJ/ mol
• If ∆Go is positive, the reactants are favoured (more reactants are present); if
it is negative, the products are more favoured (more products are present)
• Related to the equilibrium constant

∆Ho
• change in enthalpy
• Unit: J/mol or kJ/ mol
• If ∆Ho is positive, the reaction is endothermic. If it is negative, the reaction is
exothermic
 Thermodynamics (Activity 8b)

∆So
• change in entropy
• Unit: J/mol or kJ/ mol
• If ∆So is positive, the number of degrees of freedom or configuratons
increase; if it is negative, the number of degrees of freedom or
configuratin decreases

T = temperature in Kelvin
Van’t Hoff Equation

Describes the temperature dependence of K

Chemical Equations in Dissolution of Borax

A change in one of the variables that describe a system at equilibrium

produces a shift in the position of the equilibrium that counteracts the effect
of this change (Le Chatelier’s Principle)  GOAL: Relieve the STRESS

If a chemical reaction is at equilibrium and experiences a change in pressure,

temperature, or concentration of products or reactants, the equilibrium shifts
in the opposite direction to offset the change
Born-Haber Cycle

• Born-Haber cycles are enthalpy cycles that show how ionic

compounds are formed from their elements.

CONCEPTS:
• Lattice enthalpy (ΔHƟlat) - the enthalpy change when one mole of
a solid ionic compound is separated into gaseous ions under
standard conditions (endothermic)
NaCl(s) → Na+(g) + Cl-(g)

• Enthalpy of atomisation (ΔHƟatom) – the enthalpy change when

one mole of gaseous atoms is formed from an element in its
standard state (endothermic).
Na(s) → Na(g)
Born-Haber Cycle

• First ionisation energy (ΔHƟi) – the energy required to remove

one mole of electrons from one mole of gaseous atoms
(endothermic)
Na(g) → Na+(g) + e- (+496 kJmol-1)

• Bond dissociation enthalpy (E) – the enthalpy change when

one mole of bonds is broken in the gaseous state (endothermic).
Cl2(g) → 2Cl(g) (+242 kJmol-1)

• First electron affinity (ΔHƟe) – the enthalpy change when one

mole of electrons are added to mole of gaseous atoms
(exothermic).
• Cl(g) + e- → Cl-(g) (-349 kJmol-1)
Born-Haber Cycle

• Standard enthalpy change of formation (ΔHƟf) - The enthalpy

change when one mole of a compound is formed from it elements
in their standard states under standard conditions.

• Example: Na(s) + ½ Cl2(g) → NaCl(s) (-411 kJmol-1)

Sample Born-Haber Cycle
Hess Law

• Hess’s law states that total enthalpy change for a reaction is

independent of the route by which the chemical change takes place
Hess Law
Hess Law
Sample Problems (Hess Law)
Problem 1

Problem 2
Sample Problems (Hess Law)
Problem 3
Chemical Kinetics

• Chemical kinetics studies how fast a reaction takes place

• Rate Law
• The rate law is an expression relating the rate of a reaction to the
concentrations of the chemical species present, which may include reactants,
products, and catalysts

Rate = k [A]m [B]n

• [A] and [B] represent the reactants
• The exponents m and n are called “reaction orders”
• The proportionality constant k is called the rate constant
• The exponents are NOT the coefficients of the reactants!
Theories Related to Chemical Kinetics
Collision Theory
- A chemical reaction occurs when molecules collide with each other
- Usually used to describe reactions of gases

Requirements:
• Particles should collide with a certain minimum energy – activation
energy – EA

Assumptions:
• Molecules are hard spheres
• For reactions to occur, molecules
must collide
• Reactions occur only if molecules
are energetic
• Collisions should transfer certain
minimum energy
• Orientation of molecules are
proper
Role of Molecular Orientation on Chemical Reaction
Theories Related to Chemical Kinetics
Transition State Theory
TST theory assumes that chemical reaction (or any other activated
process proceeds as two-stage process:
a. Formation of activated complex
b. Decomposition of activated complex into the products of reaction;
Reaction Coordinate Diagram
 Chemical Kinetics (Elementary Steps)

Elementary Step = elementary reaction; no intermediate involved

If the reaction is an elementary step, then the exponent is the coefficient.
If not, do not assume that the exponent is the coefficient.
Chemical Kinetics

• Rates of reactions can be determined by monitoring the change in

concentration of either reactants or products as a function of time t
• NOTE: Rates of reaction are not determined by stoichiometric
relationships.

• For the reaction A  B there are two ways of measuring rate:

• the speed at which the reactants disappear
• the speed at which the products appear
• Unit: M/s
Chemical Kinetics
Chemical Kinetics (Rate)
Chemical Kinetics

• How to obtain the rate law expression

• Choose data for a target reactant in which other concentrations of other
reactants are held constant.

• Use the formula:

• order of reaction = m + n

Reactant A (M) Reactant B (M) Rate

0.10 0.10 0.40 M/ min
0.10 0.40 1.60 M/ min
0.40 0.10 0.80 M/ min

Determine: rate law, order of reaction and rate constant

Rate Law for Reaction Mechanism
• Determine slow step and fast step.
• The rate law is based on the slow step. The slow step is also the
rate-determining step.
• The orders ARE the coefficient of the reactants.
• The reactants for the rate law SHOULD be part of the over-all
reactants. If not, base it on the equation where it is found in.

• Example:

NO2  NO + O (slow)
O + NO2  O2 + NO (fast)

Over-all reaction?
Rate Law?
PRACTICE PROBLEMS

b. Write the rate law if the second

reaction is the rate-determining
step.
 POST-LAB DISCUSSIONS

• Activity 7: Bonding and Properties of Compounds

• Activity 8a: Types of Chemical Reaction
• Activity 8b: Thermodynamics of the Dissolution of Borax
• Activity 9: Factors Affecting Rates of Chemical Reactions
Activity 7: Bonding and Properties of Compounds

• Major Concepts
• Ionic compounds, when dissolved in water, exhibit conductivity
(meaning, the bond is generally ionic)
• Covalently-linked compounds (in pure form), do not exhibit
conductivity
• Partial dissociation (such as in acetic acid implies ionic
character, but is ACTUALLY related to resonance)
• Conductivity is not the same as conductance
• Conductance = reciprocal of resistance
• Conductivity = conductance of material between opposite sides of a
cube, once centimetre in each direction
Activity 7: Bonding and Properties of Compounds

• Answers to Research Questions

• Differentiate an intramolecular bond with an intramolecular bond. Is hydrogen
bond intramolecular or intermolecular? Provide examples.

• What is an induced dipole? How is an induced dipole-dipole interaction

different or similar to a dipole-dipole interaction?

• Provide at least three factors which can disrupt intermolecular bonds. Can
these factors disrupt ionic, covalent or metallic bonds? Why or why not?
Temperature  Increased temperature  disorganization of intermolecular
forces of attraction
Pressure  Increased pressure leads to increased H-bonding
Salts  competes with intermolecular forces of attraction (ion-dipole
interaction)
Activity 8a: Types of Chemical Reaction

• Major Concepts:
• Proof of Chemical Reactions
• Evolution of gases
• Precipitate
• Color formation or disappearance
• Temperature changes
• Odor or taste formation

• Kinds of Chemical Reactions

• Combustion
• Synthesis
• Decomposition
• Single Displacement
• Double Displacement
• Acid-base Reactions
Activity 8a: Types of Chemical Reaction

• Answers to Research Questions

• What happens to an ionic bond or covalent bond during a
chemical reaction
• What are the differences of chemical reactions and nuclear
reactions?
• Discuss at least five factors which affect chemical reactions.
• Temperature
• Catalyst
• Reactivity
• Concentration
• Presence of inhibitors
• Solubility
• Pressure
• Collision (Collision Theory)
• Equilibrium state
Activity 8b: Thermodynamics of the Dissolution of Borax

• Major Concepts
• Solubility of borax in water is temperature dependent.
 Activity 8b: Thermodynamics of the Dissolution of Borax
0
0 0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035 0.004

-5

y = -17696x + 39.178
R² = 0.9903
-10
ln Ksp

-15

-20

-25

-30
1/T
Activity 9: Factors Affecting Rates of Reaction

• Research Questions
• Are there thermodynamic principles which relate to rates of
reaction? Discuss each possible explanations.
• What is Le Chatelier’s Principle? In what conditions does a
chemical equilibrium change?
• Is Le Chatelier’s Principle applicable in chemical reactions in
living organisms? Why or why not?
• Le Chatelier's principle applies to the reaction of biopolymers
against equilibrium disturbances such as osmotic stress
• Le Chatelier’s principle is also applied in CO poisoning
mechanism
Activity 8b: Thermodynamics of the Dissolution of Borax

• Research Questions

Show the Born-Haber cycle of the following:

• Formation of sodium chloride from sodium and chlorine gas.
• Dissolution of calcium sulphide in water
• Dissolution of borax (in this activity)

What is the enthalpy of reaction of these processes? What are

possible reasons for the differences in these reactions?

• What is the importance of knowing the ΔG of a chemical reaction?

• What is Hess Law? How is it used to determine energy changes in

a chemical reaction?
Post-lab Notes (Research Questions)
Types of Decay