CHM1102

Lecture 25
Introduction to Thermodynamics
 Introduction to Thermodynamics
• The study of the change of energy accompanying a “process” within
a system
• a change of state (expansion),
• a change of physical state or phase (melting) or
• a chemical reaction
• Systems tend to prefer to be in a lower energy level
• Spontaneous chemical reactions tend to move from a highenergy
level to a lower energy level

• The particular part of the universe that is being studied is referred

to as the “system”, which has distinct physical boundaries
– e.g. the reactants and the products

• The “surroundings” is every other part of the universe outside the

system
Universe = System + Surroundings
 Types of Systems
Three types of systems
1. Open system:
• Allows exchange of matter and energy between the
system and its surroundings
– e.g. an open bottle of soft drink

2. Closed system:
• Allows only the exchange of energy between the
system and its surroundings, no matter is exchanged
– e.g. A corked bottle of soft drink

3. An isolated system:
• Allows neither matter nor energy to be exchanged with
its surroundings
– e.g. A thermos flask used to store cold or hot liquids/foods
 State Functions & Path Functions
• A state function is used to describe the condition (state) of
a system
• property of a system that is dependent on the value of
the property and not the means by which the system
attained this state, e.g. Altitude
• The change in state functions is only dependent on the
initial and final states not the intermediate values of getting
to this state

• A path function depends on the process or path of getting

from one value to the next value
– e.g. Work

• State functions are given symbols using upper case letters

State and Path Functions
 Work & Heat
• Energy is required to do work – “Energy is the capacity to do work”
• Work is the transfer of energy to change motion of the atoms in a
uniform manner
• Work is done when a force is moved over a distance
w = F x d (Joules)

• Work can be expansion or non expansion

• When a system expands against a pressure it does work
w = d x PexA (Pex – external pressure; A – Area)
d x A = ∆V (change of volume)
w = - Pex ∆V
(-ve sign indicates work is being done by the system, using energy)

• Heat (q) is the transfer of energy to cause a chaotic motion of the

atoms
 Work

ΔV Work
Gas expands + -
Gas compresses - +
 Heat (q)
• The transfer of thermal energy between two
bodies at different temperatures.
• Heat flow (a redundant term) increases the
thermal energy of one body and decreases the
thermal energy of the other.
 First Law of Thermodynamics
• Energy cannot be created nor destroyed but
only changed from one form to another
(Conservation of Energy Law)
• The internal energy of an isolated system is
constant (First Law of Thermodynamics)
∆U = w + q
U = internal energy; w = work; q = heat
• The sign indicates if internal energy is lost or gained by the system
• Internal energy is an example of a state function (or state variable),
whereas heat and work are not state functions.
 Enthalpy(H)
• Now if the system does some PV work
w = -P∆V
∆U = q -P∆V
q = ∆U + P∆V

• If the process is done at constant pressure

qp = ∆U + P∆V
qp is given a special name Enthalpy (H)(a state function)
∆H = ∆U + P∆V (at constant pressure)
H = U + PV

• Enthalpy is heat change at constant pressure

ΔH = Hproducts– Hreactants
 Calorimetry
• When a reaction occurs it may give off heat to the
surroundings or absorb heat from the surroundings.

• The process of giving heat to the surroundings is

called an exothermic process (-∆H, or ∆H < 0)

• The process of taking heat from the surroundings

is called an endothermic process (+∆H or ∆H > 0)

• The method used to measure this heat change is

called Calorimetry
• done by carefully tracking the temperature change during the reaction process
Calorimetry
 Calorimetry
• Regular calorimetry is done at
constant pressure so enthalpy is
determined
• Each material will increase in
temperature when a certain
amount of heat is applied or
withdrawn
• This is the heat capacity of the
material
• The amount of heat required to
cause a change of one degree per
unit mass is called the specific
heat capacity (Cs)
‘coffee cup’ calorimeter e.g. 10 kJK-1 mol-1 or 12 kJK-1 g-1
– used to experimentally
determine heat changes Cwater = 4. 184 J/g.K
 Calorimetry
• If the temperature change is ∆T ( T2-T1) for a
process

• The amount of heat q evolved is

q = -m . C . ∆T

m = mass of solution
C = specific heat capacity of solution
∆T = Tfinal - Tinitial
 Enthalpy of Phase Changes
• When a substance changes state the energy
used for that phase change is called the
enthalpy of the phase change

• Enthalpy of fusion - ∆Hf (kJ mol-1)

• Enthalpy of vaporisation - ∆Hvap (kJ mol-1)
 Enthalpy of Formation
• Standard Enthalpy of formation (∆Hf°) of a substance is the
standard reaction enthalpy for the formation of the substance
from its elements in their most stable form under standard
conditions (1atm, 298K, 1M)

• The standard state of a substance is when the substance isin

its pure form at a pressure of 1 atm

2C(s) + 3H2(g) + ½ O2(g) → C2H5OH(l) ∆Hf°= -277.69 kJmol-1

• The above reaction is a thermochemical equation
• The standard enthalpy of formation of an element in itsmost
stable form is 0 kJmol-1.e.g. ∆Hf° {O2} = O kJmol-1