Thermodynamics

Study of energy conversions between

heat and other forms e.g.. Mechanical,
chemical, electrical (burn fuel)

Concepts
SYSTEM: Region enclosed within well defined
boundaries. Outside is surroundings. Refer to eg
tempt. Of a system, work on a system etc.
Open system: Matter and energy can cross to the
surroundings and back.
Closed system: Energy can cross the boundary but
matter cannot.
Isolated system: No exchange of matter and energy
between system and surroundings.

Energy
Capacity of system to resist change or cause
change.
In physics, we talk about the capacity to do work.
However, inherent resistance to change must be
overcome in order to do work.

Thermodynamic states
Important concept. May be said to be the complete
set of thermodynamic properties of a system which
can change during a process (interactions within OR
between system and surroundings).
During a thermodynamic process, specific quantities
of heat and work are transferred to or from the
system to alter its state.
A set of thermodynamic properties define the STATE
of a system e.g.. H, P, V, T, E(internal energy).

1 Law of Thermodynamics
st

Law of conservation of energy and mass

The total energy of a system is conserved. Energy can be
transferred from one form to the other. A similar statement can
be made about mass.
Lavoisier, 1774, demonstrated that mass is conserved in
chemical reaction.
In nuclear reactions, mass may be destroyed to produce energy.
The experiments of Joule and Kelvin b/n 1843 and 1848
demonstrated the precise equivalence of total thermal energy
and mechanical work.

nd

Law of Thermodynamics

About the disorder in a system.

Part of the energy available to a system to do work may
be wasted (or lost to its surroundings).
A measure of energy unavailable to do work is referred
to as Entropy (S). It is a state variable. S is also said to
be a measure of disorder in a system.
For a reversible process at tempt. T, where Q is the
heat absorbed, S = Q/T e.g. ice melts, water boils.

3 Law of thermodynamics
rd

By definition, the entropy of a perfect crystal at

absolute zero of temperature is zero. Here, there is
no motion of atoms or molecules, zero thermal
energy or heat. There can be no disorder at this
state.

Enthalpy ( H and H)
Lab Chemical reactions usually occur in open vessels against
the constant atm pressure
The energy of this system is usually referred to as enthalpy,
H, which is a state function
When the system reacts absorbs or evolves heat and
experiences change in enthalpy, i.e.
H = H final Hinitial. H is
a state function.
For chemical reaction, H = Hprod Hreactants.
Endothermic absorbs heat from surroundings i.e. +H
Exothermic system loses energy i.e. -H

Heat of Reaction
H for chemical rxn shows as heat, work or both.
E.g. battery turns fan, work + heat. Join +ve & -ve
terminal with metal resistance wire, heat only.
When all enthalpy change appears as heat, H is
equal to Heat of Reaction at constant pressure, q p.
H = q (@ const. pressure).

Standard Conditions
Reference point needed to compare H for
different reactions. Chemists have set 25o, 1atm,
e.g.
2NH3(g) Ho = -92.38kJ at
N2(g) +3H2(g)
25oC and 1 atm pressure.
Ho is standard heat of reaction.

Hesss Law of Heat Summation

For a reaction that can be written in steps, Ho
equals the sum of values of Ho for individual
steps. E.g. C is oxidized to carbon dioxide.
When equation is reversed, sign of Ho is
reversed.
E.g. and exercise

Enthalpy diagrams- Multistep/one step

C

(s)

+ O2 (g)
Ho -110.5kJ

-393.5kJ

CO

(g)

+1/2O2 (g)

-283.0kJ

CO2 (g)

Standard heats of formation, H

Standard enthalpy of formation is heat absorbed or evolved

per mole of compound formed from its elements @ 25oC
& 1 atm pressure.
An element is in its standard state when it is at 25 oC & 1
atm. E.g.. Nitric acid formation.
When reactants react to form products, both have their
Hof
The Hreaction is therefore the difference in the sum of the
standard heats of formation of products and reactants. This
is the general form of Hesss Law

Chemical Bond Energies

When atoms bond to form molecules, energy is
released or liberated (usually as heat or light).
To dissociate a bond heat must be supplied ie
Bond dissociation energy
Examples

Bond Energy
Chemists use bond energies to
1. estimate relative stabilities of compounds
2. Predict course of chemical reactions to some
extent. Will it be
exothermic (heat releasing, -H)
or endothermic (heat absorbing, +H)?
Eg.

Predicting course of reaction

CH4 + Cl2
CH3Cl + HCl
___________________________________
Cl - Cl + 58kcal/mol
Cl. + Cl.
CH3-H + 104 kcal/mol
CH3. + H.
CH3. + Cl.
CH3Cl + 85.5 kcal/mol
H.+ Cl.
HCl + 103 kcal/mol
___________________________________
Cl2 + CH4
CH3Cl + HCl
Adding up, net H is -24 kcal/mol. In the lab this reaction is indeed
exothermic

Spontaneous Process
A nail left outdoors
Ice at room temperature
Reversible process spontaneity occurs in both
directions.
0oC
H2O(s)
H2O(l) H could be 0
For spontaneity, consider H and S
H : -ve, normally spontaneous

+ve, normally not spontaneous

At T > 0, ice melts even though endothermic

Spontaneous process
Entropy is the measure of disorder in a system
Sfinal Sinitial = either +/-S (increased randomness
or decreased randomness).
Consider dissolution of KCl in water.
6 CO2 + 6 H2O
C6H12O6 + 6 O2
Sketch entropy change with phase change

Gibbs free energy

For spontaneous change S and H are involved in affecting
the process. How do these relate?
Gibbs, J. W. (American) proposed new state function now
called Gibbs free energy or just free energy defined as G =
H TS.
For a process at const. T, change in free energy of system is
given by expression
G = H TS
The sign of G provides information about spontaneity at
constant temp and pressure as exists in the lab. ie

G
-ve G : reaction spontaneous in forward direction
+ve G : reaction is non-spontaneous in the
forward direction
G = 0 reaction is at equilibrium.
G may be said to be maximum useful work that
may be done by system on its surroundings.