CHEM 1067

Introduction to Chemistry II

Dr. Nigel John

Office: Rm 304, C1 BLDG
Office hours: Tuesdays and Wednesdays from 10 am to 11 am
Email: Nigel.John@sta.uwi.edu
 Outline

1. Required reading
-Burrows, Holman, Parsons, Pilling & Price. 2009.
Chemistry3. Introducing inorganic, organic and
physical chemistry. Oxford University Press.

- Atkins’ Physical Chemistry, 9th Edition or

- Atkins, The Elements of Physical Chemistry

2. Coursework exam #2 - Thursday 28th March, 2019, 9:00 am

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 Objectives

1. Distinguish between systems and surroundings

2. Identify and define state functions

3. Define thermodynamic variables especially the concepts of

heat (q), work (w), internal energy (ΔU)

4. Define and discuss the First Law of Thermodynamics

Chemistry3, Second edition, Chapter 13

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 Thermodynamics vs Kinetics
Thermodynamics: all about “if”

- transformation of energy specifically work and heat

e.g. when fuel burns in a furnace to provide heat;

- whether or not a process or a reaction can occur

(is there a decrease in free energy?)
The change in the free energy (∆𝐺) is the maximum amount of work
that a thermodynamic system can perform in a process at constant
temperature, and its sign indicates whether a process is
thermodynamically favourable (∆𝐺 = −𝑣𝑒) or forbidden (∆𝐺 = +𝑣𝑒).

- position of the equilibrium in a chemical reaction

In thermodynamics, we are interested in the behavior of the

macroscopic system not the individual atoms or molecules

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 Thermodynamics vs Kinetics

Kinetics: all about “how”

‒ Rate of reaction; how quickly equilibrium is achieved

‒ kinetics of a process; how to overcome the energy barrier to finish the

transformation from the starting (reactant) state to the final (product)
state.

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 Introduction to Thermodynamics

In Physical Chemistry, the Universe can be described as being

made up of System and Surroundings.

SYSTEM + SURROUNDINGS = UNIVERSE

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 Introduction to Thermodynamics

SYSTEM = Part of the world of interest; e.g. reaction vessel, electrochemical

cell (not fixed)

SURROUNDINGS = Rest of World (Universe); region outside the system

where we make our measurements

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 Introduction to Thermodynamics

• Systems can be open, closed, or isolated depending on the

boundary between the system and its surroundings

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Introduction to Thermodynamics

Types of boundaries

1. Diathermic: allows energy

transfer as heat

2. Adiabatic: prevents energy

transfer as heat

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Work, heat and the First Law

Work (w):
• Fundamental physical property in
thermodynamics

• work is done when an object is

moved against an opposing force;
transfer of energy that makes use
of organized motion.

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 Work, heat and the First Law

Energy
• (of a system) is its capacity to do work;

• when a system does work, the energy of the system is reduced and
it can do less work than before

• Energy of a system may be changed by means other than work i.e.

through changes in heat

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Work, heat and the First Law

Heat (q):
• form of energy that is
TRANSFERRED between two
systems (or system and
surroundings) by virtue of a
temperature difference;

• makes use of disorderly molecular

motion (thermal motion)

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 First Law of Thermodynamics
Relationship between different kinds of energy
• Work energy (w), heat energy (q), internal energy (ΔU)

U  U B  U A  q  w First Law of Thermodynamics

• Heat and work are equivalent ways of changing a system’s internal energy
• W > 0 or q > 0 energy is transferred to the system

• W < 0 or q < 0 energy is lost from the system

• i.e. Flow of energy w.r.t the system

Example :

• When a system releases 10 kJ of energy to the surroundings as work ( w = -10 kJ).

Then ΔU = - 10 kJ; internal energy of the system decreases

RE: ∆𝑈 = 𝑞 + 𝑤

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 First Law of Thermodynamics
• First Law of Thermodynamics: The internal energy of an isolated system is
constant
– In an isolated system, q = 0 and w = 0 therefore ΔU = 0

Conservation of energy principle

• When a chemical system changes from one state to another state,
the net transfer of energy to its surroundings must be balanced by
corresponding change in the internal energy of the chemical system (∆U).

• Energy can neither be created nor destroyed; rather, it can only be

transformed or transferred from one form to another.

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Internal Energy (U)
• In thermodynamics, the total energy of a system is called its Internal
energy (U)

U = sum of all kinetic and potential energies of all atoms, ions or

molecules in system

• For practical purposes in thermodynamics we deal only with ∆U and not

with U itself.

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 Internal Energy (U)

Any change in P, T, V and composition of a system changes the internal

energy from some state A to some state B
B UB

∆U = UB - UA
A UA

∆U is called a state function; i.e. process depends on its initial and final
state and not on the pathway (or route).

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 First Law of Thermodynamics
• For a large change occurring in small steps:
UB q w
U   dU   dq   dw U  q  w
UA 0 0

State function Not State functions

- Path dependent

Each small step is dU

UA can only be zero if at absolute
Kelvin, 0 K
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 Introduction to Thermodynamics
1. State function:
• value depends only on current state of the system and is independent of how
that state has been prepared.
• State functions do not depend on the path by which the system arrived at its
present state.
• (e.g U, H, P, V)

2. Extensive property:
• dependent on size / amount of substance in the system.
• A property that changes when the size of the sample changes.
• e.g. mass, V, U

3. Intensive property:
• physical property independent of size of the sample.
• A property that does not change when you take away some of the sample.
• e.g. temperature, melting point, boiling point, molecular weight, and density

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