Lecture 1

CHEM 1902
Thermodynamics and Electrochemistry
Dr. Peter Nelson

E-mail: peter.nelson02@uwimona.edu.jm
UWI Profile: https://www.mona.uwi.edu/chemistry/peter-nelson-0
Google Scholar: https://scholar.google.com/citations?hl=en&user=2J1dnFwAAAAJ

Recommended Text: Elements of Physical Chemistry by Peter Atkins and Julio de Paula
What is Thermodynamics?
Thermodynamics is the study of the transformation of energy into its various forms.
Energy can be defined as the capacity to do work and/or to transfer heat.
In Chemical Thermodynamics our interest is focused on energy transformations in chemical
reactions and in perfect (or ideal) gas processes.

Energy Transformations

During a chemical reaction energy is both released and absorbed; however, if the amount of
energy released is greater than that absorbed, the reaction is exothermic. Take for example
the combustion of octane; the main component of gasoline.
C8H18(l) + 12½O2(g)  8CO2(g) + 9H2O(g) + heat
A lot of heat energy is released during this reaction.
-The heat energy released is detected as a increase in temperature
-There will also be rush of hot gases coming from this reaction
These hot gases do work in pushing back the surrounding atmosphere.
Chemical Thermodynamics
Consider the following reactions

C8H18(l) + 12½O2(g)  8CO2(g) + 9H2O(g) + heat transferred and work done.

Ba(OH)2.8H2O(s) + 2NH4NO3(s) + Heat absorbed  Ba(NO3)2(s) +2NH3(g) + 10 H2O(l) + work done

Where did the energy come from in the first reaction? Was it created during reaction?
Where did the energy go in the second reaction? Was it destroyed?

Well, according to the law of conservation, energy can not be created or destroyed but changes from
one form to another.

Chemical systems store energy internally as potential (Ep) and kinetic energy (EK) .
Kinetic energy is energy of motion of molecules and or atoms in a chemical system. This type of energy
is quantized and exist as
EK = Etrans + Erot + Evib + Eele
Potential energy (in chemical systems) is stored in chemical bonds. This energy is possessed by virtue of
position. We will deal with this more later!
First Law of Thermodynamics
“When a chemical reaction occurs in a closed system the change in energy of the system must
appear as either heat (q) or work(w).”

This is a statement of the first law of thermodynamics. It should be noted that this law applies only to
closed systems.

From this statement it is clear that the energy within a system, referred to as the internal energy, U, is
given by q + w.
Also, clearly a change in the internal energy, ΔU = Ufinal - Uinitial

Note carefully that a chemical reaction, as written, represents a system that is closed because mass is
conserved.

For such systems ΔU = q + w

This means that any energy that enters or leaves the systems must be manifested as heat or work
 Heat and Work
Work is done when a body is moved some distance by a force in the direction of that force.

w=Fxd

Work is also done when a charge(Q) is moved against a potential(E); that is, w = E x Q. This is
electrical work.

Heat (q) is generally observed as change in temperature

q = mcΔT, heat released per unit mass (J/ g). c = Specific heat capacity, m = mass

q = CΔT, heat released, regardless of mass or moles (J). C = heat capacity ΔT = T2 – T1

The SI unit of energy, in whatever form it exists or in whatever mode it is transferred is the Joule.
1 Joule = 1 Newton x meter = 1 N m
Newton = Force required to give a mass of 1 kg an acceleration of 1 ms-2 = 1 kg m s-2
Specific heat capacity is given in units of J K-1mol-1 usually, but is sometimes given in J K-1 g-1. Also, 1 J = 1 Q x V
Other units of energy are caleries(c) and electron volts (eV)
 Sign Convention
Remember that the internal energy change occurring in a system is designated as U where U = Ufinal - Uinitial and,
for a closed system U = q + w.

There is a sign convention which must be followed to be consistent with the way we have designated U

For instance, consider the case where w = 0; i.e., no work is done, hence, U = q
Suppose heat energy leaves the system when the reaction occurs.
Ufinal < Uinitial
So U (= Ufinal – Uinitial) is a negative quantity; that is, U = q = negative value
Simply put, q is negative when heat leaves the system; that is, for exothermic reactions q is negative.

The sign convention which goes with this statement follows logically from the way we
have defined U:
if heat is added to the system q is +ve
if heat is given out by the system q is -ve
if work is done on the system w is +ve
if work is done by the system w is -ve
 Release or absorption of heat energy during
chemical reactions
For example propane, when burnt at 298 K and
1 atm, the heat evolved is 2220 kJ. Based on This can be done under two conditions
our sign convention q = -2220 kJ.
C3H8(g) + 5 O2(g)  3CO2(g) + 4H2O(l) Constant Pressure Constant Volume
Calorimetry Calorimetry

Quantification of the heat energy released or

absorbed is generally determined
experimentally via calorimetry. In this method,
the temperature change when a known
amount of a substance is reacted is determined
by temperature measurements, hence, the
heat release is calculated from q = mc (Tf – Ti)
once c is known.
 Work done in chemical reactions

Work is given by w = F x d. Chemical systems

can also do work. hf
For Instance, consider a reaction occurring in a closed vessel
with a moveable piston of cross-sectional area A. Imagine that
hi
the reaction causes expansion, mabe by producing a gas. The
external pressure is Pext.

Pext = F/ A so

F = Pext A , Hence, w = Pext A d Note Δh = d Application

V = A x d but if A is constant then

ΔV = A x Δh which can be rearranged to give
ΔV/ A = Δh

w = Pext A ΔV/ A
w = Pext ΔV
Work done by the system is = - pext V
Calculating work done for a chemical reaction
Let us consider the reaction we discussed on slide #2:

C3H8(g) + 5 O2(g)  3CO2(g) + 4H2O(l)

The work done by this system is = - Pext V

Unfortunately we don’t have volume data. However, the volumes can be calculated if perfect
gas conditions are assumed and using Pext as 1 atm (1 atmosphere = 101325 Pa)

The work done can also be calculated using another expression, w = -ΔnRT, where Δn represents a
change in the number of moles of gas (Δn = np –nr).

w = -(3 – 6) mol x 8.314 J K-1 mol-1 x 298 K = 7432.72 J

Note that the wok done is positive which means that work was done on the system and not
by the system!
The sign on the answer could have been figured out just by inspection. The fact that there was a decrease in
the number of moles of gas in going from reactants to products, decreased volume is expected: compression.