PHYSICAL

CHEMISTRY
SMJC 2233

The direction of chemical

reactions
The total energy of the universe is
constant, and so is the energy of any
isolated system.
But energy can change form, and this
happens in both chemical and
physical changes.
Thermodynamics, in its more complete
and quantitative form, can tell you in
which direction such changes will go.
It will not tell you how fast they will go:

First Law of
Themodynamics
any change in internal energy, U,
of a system is equal to the sum of
the work done on the system and the
heat flow into the system.
energy cannot be created or
destroyed, it can only be transformed
from one form to another
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 The First Law of Thermodynamics

There is a relationship between work (W),
Heat (q) and the internal energy (U) of a
system as follows;
U = q + W
Thus, q and W are positive if energy
transferred into the system as work or heat &
q and W are negative if energy is lost.
In another words, we view the flow of energy
as work or heat from the systems
perspective.
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Energy
The energy of a system is its capacity to do work.
When work is done on a system, its capacity to
do work is increased, so the energy of the
system is increased.
When the system does work, its energy is
reduced.
In summary, when work is done on a system
(W=positive),
so the energy increases (or
we can say, internal energy, U = positive).

The Internal Energy

The total energy of a system is called the
internal energy, U.
U is the total kinetic + potential energy of the
molecules composing the system.
The change in internal energy, U, is the
difference in internal energy between two states.
It means that, when the system changes from
initial state i with the internal energy, U i to a
final state f with the internal energy, U f;
U = Uf - Ui
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Expansion Work
Expansion work is the work arising from a change in
volume.
For example, as shown in the Figure, when a piston of
area A moves out through a distance dz, it sweeps out a
volume dV=Adz.

Expansion Work

The external pressure, Pex is equivalent to

a weight pressing on the piston, the force
opposing expansion is F=PexA.
Pex (the external pressure) is the pressure
applied on the system from outside the
system. Thus;
W

Vf

Vi

ex dV

Expansion against Constant Pressure

At a constant external
pressure throughout the
expansion;
W = - Pex V = Pex (Vi Vf)
For example, as shown in
Figure, the work done by
a gas when it expands
against
a
constant
external
pressure,
is
equal to the shaded area.
A chemical example of
this
condition
is
the
expansion
of
a
gas
formed in a chemical

Reversible Expansion
System at equilibrium are poised to
undergo reversible change.
Here, Pex is continuously changing but is
never far from the pressure of the system
itself.
In reversible expansion, Pex = Psys dP ~
Psys
Thus, dW = -Pex dV = -PsysdV
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Isothermal Reversible Expansion

The work done by a perfect gas when it
expands reversibly & isothermally is equal
the area under the isotherm (P=nRT/V).

vf

vi

rev dV
Vf

W nR
Vi

Vf
dV
nR ln( )
V
Vi

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 Question. A sample consisting of 1 mol of Argon is

expanded isothermally at 0 C from 22.4 dm3 to 44.8
dm3. Calculate work for each following processes;
reversibly;
W = - nRT ln (Vf/ Vi)
= - (1 mol) (8.314 JK-1mol-1) (273 K) ln (44.8 / 22.4) =
- 1573 J
Against a constant external pressure equal to the
final pressure of the gas;
W = -Pf V where Pf = nRT / Vf
Pf = (1 mol) (8.314 JK-1mol-1) (273 K) / 44.8 dm3 = 50.66
Jdm-3

V = Vf-Vi = 44.8 - 22.4 dm3 = 22.4 dm3

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Please do revision on:

Perfect Gas (Page 31)
Boyles Law (constant temperature)
and
Charles Law (constant pressure)
Page 32!
Homework: Page 54

Homework:
Page 104
2A.3(B)
2A.4(B)
2A.5(B)
2A.6(B)
2c.1b
2B.2(b)
2B.3(b)
2c6.b part (i)
2c7.b
2c8.b
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The Second Law of Thermodynamics

In any naturally occurring system the
entropy of an isolated system cannot
decrease.
Based on the 2nd law of thermodynamics,
heat can be transferred spontaneously
ONLY from a body at a higher
temperature to a body at a lower
temperature.
The concept of entropy is used to
describe the degree of order in a
system. The number of ways a system
can be organized can be used as a
measure of its disorder or randomness

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Heat Capacity at Constant Volume (CV)

At a constant volume; dU = dqV = CVdT

CV

For polyatomic gases, the molar heat capacity at

a constant volume is Cv,m= 25 JK-1 mol-1.
For monoatomic perfect gases, the molar heat
capacity at a constant volume, Cv,m= (3/2)R.

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Enthalpy (H)
U V

P
C P

Cp

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Question.
One mole of an ideal monoatomic gas at 25.0C is cooled and
allowed to expand from 1.00 dm3 to 10.00 dm3 against an
external pressure of 1.00 bar. Calculate the final temperature,
work, heat, internal energy change and enthalpy change of
this process. (R = 8.314 x 10-2 dm3.bar.K-1.mol-1.)

Answer;
PV = nRT
1 bar (10 dm3) = 1 mol (8.314x10-2 dm3.bar.K-1.mol-1) T
Thus; T = 120.3 K
1 bar = 105 Nm-2
Thus; 1 J = 1 Nm

w = Pext (Vi Vf) = 105 Nm-2 (1x10-3 m3 10x10-3 m3) = 9000 J

For monoatomic gas, Cv,m = (3/2)R

U = nCv,m T = 1 mol x 3/2 (8.314 J.mol-1.K-1) (120.3 K
298 K) = -2216.1 J
q = U w = -2216.1 J (- 9000 J) = 6783.9 J

H = U + PV = - 3.70 kJ
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The Enthalpy of a Perfect Gas

V nR
U V
U nR
U ng R

For an Ideal Gas the relationship between heat

capacities is given by;

Cp-Cv = nR

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Thermochemistry
The study of the energy transferred as heat
during the course of chemical reaction.
If we know U or H for a reaction, we can
predict the amount of heat the reaction can
produce.
Standard enthalpy change: The change in
enthalpy for a process in which the initial and
final substances are in their standard states.
Standard state: its pure form at 1 bar
Hess s law; The standard enthalpy change of an
o
o sum of the
o
overall
reaction
is the
standard

m
enthalpiesr of the individual
reactions minto which a
Pr oducts
Re ac tan ts
reaction may be divided.

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Entropy
Entropy is a measure of the energy dispersed in a
process.
The concept of entropy is used to describe the
degree of order in a system.
The number of ways a system can be organized
can be used as a measure of its disorder or
randomness
The second law of thermodynamics uses entropy
to identify the spontaneous changes among
permissible changes.

Entropy
Any spontaneous (natural) change in an isolated
system is accompanied by an increase in the
entropy of the system.
All spontaneous processes are irreversible
processes and Total entropy which is the sum of
the entropy of the system plus the surrounding
must be > 0.
For reversible process, S total = S sys+S
sur=0
For adiabatic change, Ssurr =0 (no heat is
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transferred to surr.)

Spontaneous Processes

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The Thermodynamics Definition of Entropy

It occurs as a result of a physical or a chemical change
(generally; a process)
It comes from the idea that
transferred as heat.

how much energy is

Why? It is because heat stimulates random motion in

the surroundings.
Work stimulates uniform motion of atoms in the
surroundings, thus it doesnt change their entropy.
The entropy of all perfect crystalline substances is
zero at T=0 ( Third Law of Thermodynamics)
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Entropy and reversibility

For a reversible process, the entropy change is
defined as:
q

rev

Reversible: a process where a tiny change in

conditions would reverse the process.
During a reversible process, the system remains
at equilibrium. (systems at eq. tends to undergo
reversible change)
Entropy generated due to irreversibility
S = Wlost /T

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On a warm evening, 27oC, Sara and Ali are

sitting outside having a coffee and watching
their young cousin, Fara playing with a ball.
Fara, who weighs 28 kg, is running after the
ball. Unfortunately she isnt looking where
she is going and runs into a tree. Fara
bounces off the tree, lands on the ground
and comes to a complete stop. Fara had a
speed of 8 m.s-1 just before she hit the tree.
What is the change in entropy of the
universe due to this collision?

In this case, Faras collision is an irreversible process , her

mechanical energy (kinetic energy) is completely lost as thermal
energy, and cannot be changed back into mechanical energy.
The change in entropy of the universe due to this collision is
given by:
S = Wlost /T
where T is the temperature and
Wlost is the work lost due to an irreversible process
The work lost due to the collision is the kinetic energy
previously had by Fara :
KE = mv2 = 28 kg (8 m.s-1) = 896 J.
The change in entropy of the universe is:
S = Wlost /T
= 896 J / 300 K
= 3.0 J.K-1.

Standard Reaction Entropy

The difference between the molar entropies of the
pure, separated products and the pure separated
reactants at their standard states at specified
temperature.

Where vj are stoichiometric numbers ( + for

products, - for reactants)

Free-energy Functions
Helmholtz free-energy A,
A = U TS
Gibbs
free-energy
important

G,

G = H TS
= U + PV TS
G= H - T S

the

most

 Criteria of spontaneous change :

dA 0 , (at constant temp. and
vol.)

dG 0 (at constant temp. and

pres.)
We are more interested in changes occurring
at constant pressure rather than constant
volume.
Chemical reactions are spontaneous in the
direction of decreasing Gibbs Energy.

Helmholtz Energy
At equilibrium, when neither the
forward nor reverse process has a
tendency to occur, is:
dAT,V = 0
The change in the Helmholtz function
is equal to the maximum work
accompanying a process at constant
temperature:
dwmax = dA
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Gibbs Free Energy

Or simply Free Energy
dwadd,max = dG, (maximum additional non-expansion
work)

wadd,max = G
rG = rH TrS (standard Gibbs energy of reaction)
A criterion for equilibrium is that the total Gibbs Free
Energy of a reaction is at a minimum.
A reaction in the direction of decreasing G is spontaneous
A reaction in the direction of increasing G is not
spontaneous

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34

35

Equilibrium constant

Example

Summary
Thermodynamic Properties : U,
H, S, A, G
First Law uses internal energy to
identify permissible changes.
Second Law uses entropy to
identify spontaneous changes among
those permissible changes.