ENTROPY

Why do things happen the way that

they do?

 Thermodynamics deals with the laws

of heat energy, and the transfer of it
to other types of energy
1st law of thermodynamics:
2nd law: the entropy always increases
in the transformation of energy

 ENTROPY (S): random dispersal of

molecules and energy quanta between
molecules
In simple terms: measure of the order or
disorder in a system
Refers to the distribution of the particles
and also the ways of distributing the
energy of the system in all of the available
energy levels
Units: Jmol-1K-1

E.g. diffusion

 Ways in which energy can be

distributed in a diatomic molecule;
Translational motion: moving from
one place to another
Rotational motion: molecule spins
Vibrational motion: moves about the
same point

Changes of entropy with change of state

Entropy=
0
Perfectly
ordered
crystal

Entropy in chemical reactions

The natural direction of change is the
one that gives an INCREASE in
ENTROPY

Examples:
When large molecules break down into
smaller molecules--> entropy increases
WHY?
Because there are far more ways of
arranging several small molecules than
one macromolecule

Previously on entropy:
Entropy increases when

Regular arrangement
of particles in solids

Less regular arrangement;

more disorder in liquids

SOLIDS MELT

Irregular arrangement;
some disorder in liquids

Random nature and disorder

of particles in a gas

LIQUIDS BOIL

Regular arrangement in
an ionic crystal lattice

Ions dissociate in water;

there is less order

IONIC SOLIDS DISSOLVE IN WATER

Particles in gases move in a

random way. The more gas
molecules there are, the greater
the degree of randomness.

THE MOLES OF GAS INCREASE

Lower temperature; less

energy

Higher temperature; more

energy and more disorder

THE TEMPERATURE INCREASES

 Gas evolution
(NH4)2CO3(s) + 2CH3COOH(aq) 2CH3COO(aq) + 2NH4+(aq)
+ CO2(g) + H2O(l)

H +ve a solid
othermic reaction producing

2Mg(s) + O2(g) 2MgO(s)

H -ve

ndothermic reaction of two solids

2NH4Cl(s) + Ba(OH)2.8H2O(s) BaCl2.2H2O(s) + 2NH3(g) +
8H2O(l)

1. NH4NO3(s) + aq. -- > NH4+ (aq) + NO3(aq) rH=+

. Entropy of the system?
. Increases
. That is:
In solid, particles are in fixed positions but
Become free to move around when in
solution
Level of disorder increases

2. (NH4) 2CO3 (s) + 2CH3COOH (aq) -- >

2CH3COO- (aq) + 2NH4+ (aq) + CO2
(g) + H2O (l)
rH=+
. Entropy ?
. Increases

3. 2Mg (s) + O2 (g) -- > 2 MgO (s)

rH=-ve
Entropy?
Decreases
4. 2NH4Cl (s) + Ba(OH) 2.8H2O(s) -- >
BaCl2.2H2O (s) + 2NH3 (g) +
8 H2O rH=+
. Entropy?
. Increases

Question 1: Suggest whether the following processes

involve an increase or decrease in entropy of the
system and in enthalpy. Explain your answers.
MgCl2(s) + aq Mg2+(aq) + Cl(aq)
2H2(g) + O2(g) 2H2O(l)
H2O(l) H2O(g)
2Na(s) + Cl2(g) 2NaCl(s)
NH4Cl(s) NH3(g) + HCl(g)

 Spontaneous reactions
( enthalpy and entropy )

Calculating entropy changes

E.g.
2Na (s) + Cl2 (g) -- > 2NaCl (s)
entropy decreases
How can a change in which there is a
decrease in entropy of the system be
spontaneous?
Entropy of the surroundings has to be
considered in addition to the system

 Hence, TOTAL entropy change has to

be measured, to determine whether
the reaction is spontaneous or not.

rStotal= rSsys + rSsurr

rSsys= sum of standard molar entropies of
Products
sum of standard molar entropies of
Reactants

Standard molar entropy: entropy per mole

for a substance under standard

e.g:

Calculate the standard entropy change

for the thermal decomposition of
calcium carbonate. Explain your
answer.
CaCO3 (s)
CaO (s) +
CO2 (g)
Std entropy/

+92.9

+39.7

+213.6

J/K/mol
ANSWER: +160 JK-1 mol-1
Positive value for entropy change shows

Entropy change of the surroundings

Determined by the size of the enthalpy change
rH

temperature (T in Kelvin)

The relationship is :

rSsurr =

-rH reaction / T

For an EXO reaction -- > rSsurr POSITIVE

For an ENDO reaction -- > rSsurr NEGATIVE

In summary;

rStotal= rSsys + rSsurr

rSsys=S [Products] S
[Reactants]

rSsurr = - rH reaction / T
A reaction will be feasible if the
TOTAL entropy change is POSITIVE

Summary:
Entropy:
Measure of the no. of ways that particles
can be arranged and the
No. of ways that the energy can be shared
out between the particles

So the particles naturally move to try

to increase the entropy
E.g: a gas spontaneously diffusing
across a room

 Energy can be measured in quanta- these are

fixed packages of energy
The more energy quanta a substance has, the
more ways they can be arranged and so the
greater the entropy
If you raise the temperature of a substance, you
increase the energy of its particles
The higher the temperature, the more energy
quanta a substance has and the more ways
these quanta can be distributed -- > HIGHER
ENTROPY

 rStotal= rSsys + rSsurr

rSsys=S [Products] S
[Reactants]

rSsurr = - rH / T
A reaction will be feasible if the

NOTE:
rSsurr = - rH reaction / T
In an exothermic reaction rH is
negative, so rSsurr is always POSITIVE
In an endothermic reaction rH is
positive, so rSsurr is always NEGATIVE
At Higher temperatures,rSsurr gets
smaller
As a result, it makes a smaller

Feasibility, stability & inertness

Spontaneous changes occur IF total entropy
change is POSITIVE

i.e. rStotal

> zero

It is possible even if one of the

entropy is NEGATIVE
Hence, feasibility relates to both
enthalpy and entropy changes

Exothermic
reaction
are
thermodynam
ically
More
favourable

Endothermic
reactions
are
thermodynam
ically
More
favourable

 A high activation energy barrier

may prevent a reaction starting, as in
the methane and oxygen example. In
such cases, the reactants are
kinetically stable or kinetically
inert (unreactive).

 Energy must first be provided to start

such reactions, for example:
A spark

Heat ( as in the decomposition of

CaCO3 above)
Light (visible or UV).

Key factors for the feasibility of a

rxn are:

rS

sys

rH of the surroundings
Temp in Kelvin
This is why a chemical reaction that
does not happen at room temp. may
become feasible as
Page: 10

T increases

The table below shows the various possibilities.

Surrounding

1
2
3
4

system

Enthalpy change
Entropy change
Feasible?
( H)
(S)
Exothermic
Increase
in Reaction WILL occur
entropy
Endothermic
Decrease
inReaction will NEVER occur
entropy
Endothermic
Increase
in
Reaction can occur
entropy
Exothermic
Decrease
in
Reaction can occur
entropy

 Exothermic reactions that are accompanied by an

increase in entropy of the system will always
happen spontaneously.
Example: C2H5OH(l) + 3O2(g) 2CO2(g) +
3H2O(g) H -ve
Total entropy change is positive, so the
reaction is feasible.

 Endothermic reactions that are

accompanied by a decrease in
entropy of the system will never
happen spontaneously.
Example: CO2(g) C(s) + O2(g)
H +ve

Total entropy change is negative, so the reaction is

not feasible.

 Endothermic changes that are accompanied

by an increase in the systems entropy will
be spontaneous if the temperature is
sufficiently high.
Example: water boiling: H2O(l) H2O(g)

As the temperature increases,

Ssurrincreases (becomes less negative),

Exothermic changes that are accompanied by

a decrease in the systems entropy will be
spontaneous if the temperature is sufficiently
low.
Example: steam condensing: H2O(g) H2O(l)

As the temperature decreases, Ssurrincreases,

therefore, the lower the temperature, the

Stabilities of reaction
A chemical rxn is feasible when rStotal
is positive.
BUT it does not tell us anything
about the HOW FAST the rxn is.
A high Ea barrier may prevent a rxn
from starting ; hence it is said that
reactants are kinetically stable or
inert
Therefore, energy must be provided
to start such rxns in the form of:

Calculation of minimum temperature

rStotal= rSsys + rSsurr
rStotal= rSsys + (-rH / T )
at minimum temp, rStotal is taken
as zero

At minimum temperature, Stotal is

taken as zero
0 = Ssys + Ssurr (-H/ T)

T = +Hreaction/ Ssys

Question 3
The decomposition of Zinc carbonate is shown in the reaction.
ZnCO3(S) ZnO(s) + CO2(g)
The values for Ssys and Ssurr are +175 J mol1 K1and 238 J
mol1 K1, respectively.
Show that the reaction is not spontaneous at 298 K.

Calculate the lowest temperature at which the reaction is

spontaneous.

Question 4:
Magnesium burns in air according to the following
equation.
2Mg(s) + O2(g) 2MgO(s)
H = 1203.4 kJ mol1
The standard entropy values are given below
Show, by calculation, that this reaction is spontaneous at
298K.

Enthalpy, Entropy and Solubility

When ionic solids, such as sodium chloride dissolves

in a polar solvent, there are
two separate enthalpy
changes are involved

Lattice energy

the solid must separate into

individual ions to dissolve
(an endothermic change).

Hydration enthalpy

the separated ions interact

with the surrounding polar
solvent, such as water (an
exothermic change).

Dissolution of NaCl

Standard Lattice Enthalpy, Hlattice

M+(g) + X-(g)

MX(s)

The heat energy given out or released

(exothermic enthalpy change), when one
mole of an ionic crystal lattice is formed
from separate gaseous ions under standard
conditions.
Standard Enthalpy of Hydration, Hhyd
The heat energy given out when one mole of
gaseous ions dissolve in water under standard
conditions.

M+(g) + aq
M+(aq)

Standard Enthalpy of Solution,

Hsol
The enthalpy of solution is the enthalpy change
when one mole of a compound is dissolved in
excess water to form an infinitely dilute solution
under standard conditions.

MX(s) + aq
(aq)

M+(aq) + X-

Question 6
Find the combined enthalpies of hydration of sodium and
chloride ions using Hesss cycle and also draw the energy
level diagram.
Hsolutionfor NaCl(s) = + 10 KJmol-

Hesss cycle

Hlattice for NaCl(s) = -780 KJmol-1

Hsolution
Negative
exothermic change

Positive endothermic
change

Dissolution is favourable

Dissolution is not favourable

however it is favoured by
increase in entropy

Hsolution is positive therefore endothermic change

so dissolving is not favored.
BUT IT DISSOLVES. WHY?????
Because there is an increase in entropy.

These two changes (enthalpy and entropy) can

be combined mathematically to give an
important term known as the free energy
change, G.

 It is also known as Gibbs free

energy.

Question 5
Use the following enthalpy and entropy data to predict whether
the substances will dissolve at a temperature of 298K.
Substanc Hsolution/
e
KJmol-1
Lithium
chloride
Sodium
chloride
Silver
chloride
Magnesiu
m
chloride

-37
+4

Ssystem/
Jk-1 mol-1
+11

Solubility
(Yes/No)
YES

+43
YES

+66
-91

+33
-213

NO

YES

Factors affecting the enthalpy of

hydration and the lattice energy
Ionic charge
larger charge
more attraction between the ions
more exothermic lattice energy
more negative lattice
enthalpy/enthalpy of hydration

 Example: NaCl has Hlatt =

-780kJmol-1
MgCl2 has Hlatt = -2526kJmol-1
Lattice energy is greater for
magnesium chloride as its charge
(+2) is greater than that of sodium
(+1)

 Ionic radii
smaller ionic radii
more attraction between the ions.
more exothermic lattice enthalpy
more negative lattice enthalpy /
enthalpy of hydration

 Example: Sodiums ionic radius is

bigger than magnesiums.
WHY?
because Mg has one
more proton which
has a stronger
positive nuclear
attraction to its
electrons and
therefore magnesium
will have a more