The Effect of Temperature on

Spontaneity
Endothermic rxn: heat flow from surrounding to
system
Exothermic rxn: heat flow from system to
surrounding

Heat flow to and from the system affects the

entropy of the surrounding
(NOTE: SPONTANEITY deals with whether a reaction is spontaneous
or non-spontaneous)

 Heat flow will affect the entropy of the

surrounding DEPENDING ON THE
TEMPERATURE at which the process happens
The significance of heat flow to and from the
surrounding will be GREATER at lower
temperature, i.e., the entropy of the
surrounding will change significantly if the
temperature (at which the reaction happens)
is lower.

Characteristics of Entropy, S
1. The sign of Ssurr depends on the direction of the heat
flow
If the temperature is constant,
a. An exothermic reaction will release heat to the
surrounding which will increase molecular disorder of
the surrounding thus increasing the entropy of the
surrounding, giving a positive Ssurr
b. An endothermic reaction will absorb heat from the
surrounding which will decrease the molecular
disorder of the surrounding thus decreasing the
entropy of the surrounding, giving a negative Ssurr

Entropy and Spontaneity

ssystem Ssurrounding

+
+
-

+
+

suniverse = ssystem +
Ssurrounding

Is the process
spontaneous?

+
-

YES

?
?

NO (but if you reverse

process it will be
spontaneous)
YES but only if the
ssystem >> ssurrounding
YES but only if
ssurrounding >> Ssystem

Suniverse has to be POSITIVE for a process to be spontaneous

2. Magnitude of Ssurrounding depends on temperature

Ssurrounding =

heat flow
temperature

ssurrounding is directly proportional to the heat flow

but inversely proportional to the temperature
ssurrounding can be expressed in terms of the
enthalpy of the system, Hsystem. If we consider a
process occurring at CONSTANT PRESSURE,
Hsystem = qp (Note:recall calorimetry)

If we consider a condition at constant pressure and constant

temperature (in Kelvin),
Ssurrounding =

system

(NOTE: The minus sign is needed because we are looking at the entropy
change of the surrounding but we are using the enthalpy change of the
system)

For an EXOTHERMIC REACTION, Hsystem is negative so the

Ssurrounding is positive, i.e., heat flows from system to
surrounding (negative Hsystem ) which will increase the
entropy of the surrounding (positive ssurrounding)
Ssurrounding =

system)
T

For an ENDOTHERMIC REACTION, Hsystem is positive so the

Ssurrounding is negative, i.e., heat flows from surrounding
to system (positive Hsystem ) which will decrease the
entropy of the surrounding (negative ssurrounding)

Ssurrounding =

system)
T

e.g. In metallurgy of antimony, the pure metal is recovered

via different reactions, depending on the composition of
the ore. For example, iron is used to reduce the antimony in
sulfide ores:
(a) Sb2S3(s) + 3Fe(s) ---> 2Sb(s) + 3FeS(s) H= -125 kJ
Carbon is used as the reducing agent for the oxide ores:
(b) Sb2O6(s) + 6C(s) ---> 4Sb(s) + 6CO(g) H= 778 kJ
Calculate ssurrounding for each reactions at 25oC at 1 atm.

Solution:
1. Use

Ssurrounding =

system)
T

2. Convert 25oC to K, T= 25 + 237 = 298 K

3. For reaction (a), Ssurrounding = 419 J/K, i.e., the
reaction is exothermic so heat flows to the surrounding
which increases the entropy of the surrounding.
4. For reaction (b), Ssurrounding = -2.61 x 10 3 J/K, i.e., the
reaction is endothermic so heat flows to the system
which decreases the entropy of the surrounding.

Calculating for entropy

The entropy of a perfect crystal at 0 K is zero.
This is an ideal value which is taken as a
standard but never actually observed.

The entropy (disorder)of a non-ideal substance

increases with temperature because of the
increase in the random vibrational motion.

Since the S is zero for a perfect crystal at 0K, the

standard entropy value, So, for substance at a
particular temperature can be calculated by
knowing its temperature dependence.
The standard entropy value So represents the
increase in entropy when a substance is
heated from 0 K to 298 K at 1 atm.

Entropy is a state function of the

system like enthalpy.
The entropy change (So) for a given chemical
reaction can be calculated from the standard
entropy values (So) of the products and
reactants
So reaction = S nproduct Soproduct - S nreactant Soreactant

Calculate the So for the reduction of Aluminum oxide

by hydrogen gas: Al2O3(s) + 3H2(g) ---> 2Al(s) + 3H2O(g)
Consider the following standard entropy values:
Substance So (J/K-mol)

Substance So (J/K-mol)

Al2O3(s)

51

Al(s)

28

H2(g)

131

H2O(g)

189

Solution:
1. Use So reaction = S nproduct Soproduct - S nreactant Soreactant
2. So reaction = [2 mol Al (28 J/K-mol)+3 mol H2O (189
J/K-mol)] [1 mol Al2O3 (51 J/K-mol)+ 3 mol H2 (131
J/K-mol)] = 179 J/K

Summary
Entropy, S, is a measure of randomness.
The second law of thermodynamics states that in any
spontaneous process, there is ALWAYS an increase in the
entropy of the universe.
Suniverse = Ssystem+Ssurrounding
Suniverse is positive, there is an increase in the entropy of
the universe, and the process is spontaneous. Suniverse is
negative, theres a decrease in the entropy of the universe,
the REVERSE process is spontaneous.
standard entropy value, So, for a substance can be known
The change in the entropy of a chemical reaction can be
calculated from So of products and reactants in their
standard states
So reaction = S nproduct Soproduct - S nreactant Soreactant

Free Energy, G
Free energy, G, is another thermodynamic function
that is related to spontaneity and the temperature
dependence of spontaneity. It is defined as :
G = H TS
(Note: H is enthalpy, T is the Kelvin temperature & S is the entropy)

At constant temperature T, the change in the free

energy of the system is
Gsystem = Hsystem -T Ssystem

We can manipulate this equation to see how it

relates to spontaneity.

If we divide the equation by the temperature T,

Gsystem = Hsystem - T Ssystem
T
Gsystem
T

T
=

Hsystem
T

- Ssystem

then multiply both sides by -1

-

Gsystem
T
Gsystem
T

=-

Hsystem
T

+ Ssystem

= Ssurrounding + Ssystem = Suniverse

Gsystem
T

= Suniverse at constant T & P

The equation above indicates that a process carried out at

constant temperature & pressure will be SPONTANEOUS
only if G is NEGATIVE, i.e., a process at constant T & P is
spontaneous in the direction which decreases the free
energy.
For a chemical reaction, spontaneity will depend on the
temperature and which state function will control the
reaction based on the relationship given by
Gsystem = Hsystem -T Ssystem

G = H TS
Because 0 H 0 and 0 S 0, there are four
possibilities for G.
H

+
+

S
G
Reaction spontaneity
+

Spontaneous at all Ts.

Temp dependent
Spont at low Temp.
+
Temp dependent
Spont at high Temp.

+
NON Spont at all Ts.

Free energy and chemical reactions

Standard free energy change,Go, is the change in
the free energy if the reactants in their standard
states are converted to the products in their
standard states.
e.g. N2 (g) + 3H2(g) 2NH3(g)

Go = -33.3 kJ

Change in the free energy when 1 mole of

nitrogen gas at 1 atm reacts with 3 moles of
hydrogen gas at 1 atm to produce 2 moles
gaseuous ammonia at 1 atm.

Standard free energy change,Go is not measured like

enthalpy or entropy. It is calculated from other measured
quantities. We can use the relationship Go = Ho -T So to
calculate for the standard free energy

e.g.
C(s) + O2 (g) ---> CO2 (g) Ho=-393.5 kJ So= 305 J/K
Calculate Go at 25oC.
Solution:
1. Convert temperature to K: T= 25+273= 298 K
2. Go = Ho -T So=(-3.935x105 J)-[(298K)(305 J/K)]
= -3.944x105J
or -394.4 kJ/mol CO2 formed.

e.g. Consider the following:

2SO2(g) + O2(g) ---> 2SO3(g)
The above reaction was carried out at 25oC at 1
atm. Calculate Ho, So & Go using the following
data:
Substance
SO2 (g)
SO3 (g)
O2(g)

Hof (kJ/mol)
-297
-396
0

So (J/K-mol)
248
257
205

Solution: 2SO2(g) + O2(g) ---> 2SO3(g)

1. Ho = S nproduct Hof product - S nreactant Hof reactant
Ho = [2mol SO3(g) x(-396 kJ/mol)]-[2mol SO2(g)x (297 kJ/mol)]+[1mol O2(g)x(0 kJ/mol)]
Ho = -792 kJ + 594 kJ = -198 k
2. So = S nproduct So product - S nreactant Soreactant

So = [2mol SO3(g) x(257 J/K-mol)]-[(2mol SO2(g)x 248

J/K-mol)+(1mol O2(g)x 205 J/K-mol)]
= 514 J/K - 701 J/K = -187 J/K

3. Go = Ho -T So
1 kJ
= -198 kJ ( 298 K)(-187 J/K)(
)
1000 J
= -142 kJ

Bond energy and enthalpy

Chemical reactions involves breaking and forming of

bonds. We can use bond energy values to calculate
for the approximate energies for reactions.
Consider the reaction below:
H2(g) + F2(g) ---> 2HF(g)
This reaction involves BREAKING 1 H-H bond and 1 F-F
bond and FORMING 2 H-F bonds.
Bond BREAKING requires energy to be ADDED to the
system (endothermic process, positive sign)
Bond FORMING requires energy to be RELEASED to the
surrounding (exothermic process, negative sign)

We can then express the change in energy of the

reaction based on bonds broken (positive sign)
and bonds formed (negative sign)
H = Sn x D(bonds broken) - Sn x D(bonds formed)
where
D = represents the bond energy per mole of
bonds; always a POSITIVE VALUE given in kJ/mol
n = moles of a particular type of bond

e.g. Consider the formation of HF:

H2(g) + F2(g) ---> 2HF(g)
Bond
H-H
F-F

Average Bond energy

(kJ/mol)
432
154
565

H-F
Solution:
H = Sn x D(bonds broken) - Sn x D(bonds formed)
= [1mol H-H (432 kJ/mol) + 1mol F-F (154 kJ/mol)][2 mol H-F (565 kJ/mol)]
= -544 kJ
When 1 mol H2(g) reacts with 1 mol F2(g) to form 2 mol
HF(g), 544 kJ of heat should be released.

Using bond energies, calculate the H for the reaction of

methane with chlorine and flourine to give Freon-12.
CH4(g) + 2Cl2(g) +2F2(g) ---> CF2Cl2(g) +2HF(g) + 2HCl (g)
Solution:
1. Identify bonds broken and formed.
Bonds broken:
1 mol CH4 has 4 C-H bonds, so there are 4 mol C-H bond broken
per 1 mol of CH4
2 mol Cl2 has 2 mol Cl-Cl broken
2 mol F2 has 2 mol F-F broken

Bonds formed:
1 mol CF2Cl2 has 2 C-F bond & 2 C-Cl bond, so there are 2 mol C-F
bond formed & 2 mol C-Cl bond formed per 1 mol of CF2Cl2
2 mol H-F bond formed
2 mol H-Cl bond formed

2. Calculate energy involved in bond breaking and bond

formation using bond energies in kJ/mol.
Bond

Bond
energy
(kJ)/mol

Bond

Bond
energy
(kJ/mol)

Bond

Bond
energy
(kJ/mol)

Bond

Bond
energy
(kJ/mol)

C-H

413

C-F

485

C-Cl

339

Cl-Cl

239

F-F

154

H-F

565

H-Cl

427

CH4(g) + 2Cl2(g) +2F2(g) ---> CF2Cl2(g) +2HF(g) + 2HCl (g)

Bonds broken:
CH4: 4 mol (413 kJ/mol) = 1652 kJ
2Cl2: 2 mol (239 kJ/mol) = 478 kJ
2F2: 2 mol (154 kJ/mol) = 308 kJ
TOTAL ENERGY for bonds broken: 2438 kJ

CH4(g) + 2Cl2(g) +2F2(g) ---> CF2Cl2(g) +2HF(g) + 2HCl (g)

Bonds formed:
CF2Cl2: 2 mol C-F (485 kJ/mol)= 970 kJ
: 2 mol C-Cl (339 kJ/mol)= 678 kJ
2HF(g) : 2 mol H-F ( 565 kJ/mol)= 1130 kJ
2HCl(g) : 2 mol H-Cl (427 kJ/mol)= 854 kJ
TOTAL ENERGY for bonds formed: 3632 kJ

3. Calculate for the H for the formation of Freon-12.

H = Sn x D(bonds broken) - Sn x D(bonds formed)
H = 2438 kJ 3632 kJ = -1194 kJ
There is 1194 kJ of energy released per mole of
CF2Cl2(g) formed.