LINGLING

PIM

THERMO-
CHEMISTRY
ADVANCE
CHEMISTRY
 LAW OF
THERMODYNAMIC
 WWW.LAW.COM

LAW OF THERMODYNAMIC
FIRST LAW SECOND LAW
the First Law of the Second Law of
Thermodynamics states Thermodynamics states
that energy cannot be that every energy transfer
created or destroyed. that takes place will
It can only change form or increase the entropy of
be transferred the universe.
from one object to
another.
 THERMO-
CHEMISTRY
 THERMOCHEMISTRY
• Is the study of heat change in chemical reactions.

• It qualitatively and quantitatively describes the energy changes during

chemical reactions.

• It involves the notion of a system and its surroundings.

• System ; the part of the universe focusing attention.
• Surrounding ; everything around.

• The transfer of heat, work performed by the object or the combination of

heat and work can change the energy of an object.
 ENTHALPY,
ENTROPY,
FREE ENERGY.
 ENTHALPY, ENTROPY, FREE ENERGY

● Enthalpy (H) is used to quantify the heat flow into or out of a system in a
process that occurs at constant pressure.
○ At constant pressure, heat flow (q) and internal energy (U) are related to the
system’s enthalpy (H).
■ Exothermic process is any process that gives off heat meaning it
transfers thermal energy from the system to the surroundings.
■ Endothermic process is any process in which heat has to be supplied
to the system from the surroundings.
 ENTHALPY,ENTROPY,FREE ENERGY

● First law of thermodynamics is that energy can be converted from one

form to another, but cannot be created or destroyed.
○ ΔUsystem + ΔUsurroundings = 0 or ΔUsystem = - ΔUsurroundings
○ ΔUsystem = q+w
■ ΔU is the change in internal energy of a system.
■ q is the heat exchange between the system and the surroundings
■ W is the work done on or by the system.
 ENTHALPY,ENTROPY,FREE ENERGY

● Calorimetry is the science of determining the change in energy of a

system by measuring the heat exchange of the system with the
surroundings.
○ Calorimeter; the device produced or absorbed heat during chemical
reaction or combustion process.
 ENTHALPY,ENTROPY,FREE ENERGY

● Q=mcΔT
○ m= mass
○ c= specific heat
■ A substance is the amount of heat (q) required to raise the
temperature of one gram of the substance by one degree Celsius.
○ ΔT= change in temperature
○ Q= heat capacity
■ Is the amount of heat (q) required to raise the temperature of a given
(m) of the substance by one degree Celsius.
 ENTHALPY,ENTROPY,FREE ENERGY

● Hess’ Law states that, if a reaction can take place by

more than one route and the initial and final conditions are
the same, the total enthalpy change is the same.
 ENTHALPY,ENTROPY,FREE ENERGY
Entropy
● Is the measurement of randomness or disorder of a system. The SI Unit of
entropy is J/k
● ΔS = ΔSf - ΔSi
○ The change from initial to final results in an increase in randomness.
■ ΔSf > ΔSi, ΔS>0
■ Increasing temperature,volume, molecular complexity or atomic weight
increases entropy.
■ Phases changes results in an increase in energy,
■ Changing in the number of moles of gas.
● Second law of thermodynamics is that the entropy of the universe increases in
a spontaneous process and remains unchanged in an equilibrium process.
 ENTHALPY,ENTROPY,FREE ENERGY
Gibbs free energy
● Is the free-energy change for a reaction when it occurs under
standard-state conditions.
● Standard free of formation is the free-energy change that occurs when 1 mole
of the compound is formed from its elements in their standard states.
○ It is stable in any element when it equals 0
● ΔG = ΔHsys - TΔSsys
○ For a constant temperature and constant pressure process.
○ ΔG< 0 The reaction is spontaneous in the forward direction.
○ ΔG> 0 The reaction is nonspontaneous as written. The reaction is
spontaneous in the reverse direction.
○ ΔG= 0 The reaction is at equilibrium.
 SPONTANEOUS
related to
enthalpy, entropy
& gibbs free energy
 SPONTANEOUS REACTION
• Spontaneous reaction is both physical and
chemical reactions that can occur by itself without
any external energy.

• Nonspontaneous reaction is a reaction that need

external energy to occur.

• Spontaneous reaction release free energy which

will further be available to do work. To determine
the spontaneity of the system, the enthalpy and
entropy are the determining factors.
 SPONTANEOUS REACTION

• The second law of thermodynamics says that the entropy of the

universe always increases for a spontaneous process:
• ΔSuniverse = ΔSsystem + ΔSsurroundings > 0
• At constant temperature and pressure, the change in Gibbs free
energy is defined as
• ΔG = ΔH − TΔS
• Reaction will be spontaneous when ΔG < 0
 SPONTANEOUS REACTION
The sign affecting spontaneity
ΔG = ΔH − TΔS

ΔH ΔS T ΔG
+ + High Spontaneous (-)
+ - - Nonspontaneous (+)
- + - Spontaneous (-)
- - Low Spontaneous (-)
 EXAMPLES
of
Thermodynamics, Enthalpy,
Entropy, Free Energy,
Spontaneous .
 WWW.EXAMPLE.COM

THERMOCHEMISTRY
A 6.22 kg piece of copper metal is heated from 20.5 Celsius to
324.3 Celsius. Calculate the heat absorbed (in kJ) by the metal.

c = 0.38 J/g Celsius

Qsystem = (6.23x 1000 g)(0.38 J/g Celsius)(324.3-20.5 Celsius)

= 718061.68 J
= 718.06 kJ

The heat absorb is 718.06 kJ

 WWW.EXAMPLE.COM

Enthalpy, Entropy,
Free Energy, Spontaneous
Calculate the standard enthalpy change, entropy change and Gibbs free
energy change and determine the spontaneity of the reaction at 298 K for
each of the following reaction by using data below.

2Fe3O4(s) + ½ O2(g) ----> 3 Fe2O3(s)

Substance ΔG ΔH ΔS
Fe3O4(s) -1015.4 -1118.4 146.4
O2(g) 0 0 205.14
Fe2O3(s) -742.2 -824.2 87.40
Find the Enthalpy (ΔH)

ΔHrxn = ΔHproduct - ΔHreactant

= 3Fe2O3(s) - [ 2Fe3O4(s) + ½ O2(g) ]
= 3(-824.2) - [ 2(-1118.4) + ½(0) ]
= -235.8 KJ/mol

The enthalpy of the reaction is -235.8 KJ/mol

Find the Entropy (ΔS)

ΔSrxn = ΔSproduct - ΔSreactant

= 3Fe2O3(s) - [ 2Fe3O4(s) + ½ O2(g) ]
= 3(87.4) - [ 2(146.4) + ½(205.14) ]
= -133.17 J/molᐧK

The entropy of the reaction is -133.17 J/molᐧK

Find the Gibbs Free Energy (ΔG)

ΔGrxn = ΔGproduct - ΔGreactant

= 3Fe2O3(s) - [ 2Fe3O4(s) + ½ O2(g) ]
= 3(-742.2)- [ 2(-1015.4) + ½(20) ]
= -195.8 KJ/mol

The gibbs free energy of the reaction is -195.8 KJ/mol

Determine the Spontaneity

ΔG = ΔH − TΔS
= -235.8KJ/mol - (298K)(-133.17 J/molᐧK)
= -39920.46 KJ/mol

The reaction is spontaneous because ΔG < 0

 Real Life Example of Enthalpy, Entropy, Free Energy, and Spontaneous

Enthalpy Entropy
Endothermic : Ice melting Increase : Ice melting
Exothermic : Raining Decrease : Racking the leaves

Gibbs Free Energy

Spontaneous reaction & Nonspontaneous reaction
Iron rusted Water freezing
Waterfall Electrolysis of water
Smell diffuse
https://www.ck12.org/book/ck-12-chemistry-intermediate/section/20.2/

https://docs.google.com/document/d/1hhINvvG4OslrfslB_KAxADZ7-iYkS
0e00roFwHu9lVE/edit

https://www.khanacademy.org/science/ap-biology/cellular-energetics/ce
llular-energy/a/the-laws-of-thermodynamics

https://classroom.google.com/u/1/c/MTIxOTgyODkzNjg1/m/MjM0MDM2OD
AwMzcz/details