THERMODYNAMICS AND

EQUILIBRIA
CHE 434
PROCESS CHEMISTRY

5.1 First law of

thermodynamics

Basic concepts
Energy: capacity to do work
Law of conservation of energy: the total quantity
of energy in the universe is assumed constant
Chemical reaction absorb/release energy in
form of heat
Heat: transfer of thermal energy between two
bodies that are at different temperatures

 Thermochemistry: study of heat change in

chemical reactions
System : specific part of the universe that
is of interest to us
Surroundings: the rest of the universe

 Open system: can

exchange mass and
energy (heat) with
surrounding

Closed system:
allows transfer of heat
but not mass

matter

surroundings

system
energy

matter

surroundings

system
energy

Isolated system:
does not allow transfer
either mass or energy

matter
system
energy

surroundings

 EXOTHERMIC PROCESS a process

that releases energy as heat into its
surroundings.
All combustion reactions are exothermic.
ENDOTHERMIC PROCESS process
which energy is acquired/absorbed from
its surroundings as heat

 Thermochemistry is part of a broader

subject called thermodynamics, which is
the scientific study of the interconversion
of heat and other kinds of energy.
The laws of TD provide useful guidelines
for understanding the energetics and
direction of processes

First law of thermodynamics

Energy can be converted from one form to
another, but cannot be created nor destroyed
Validity tested by measuring the change in
internal energy, E.
E = Ef Ei

 E has two components:

kinetic energy: motion/movement of e- in
molecule
potential energy: attractive and repulsive
interactions, e--nuclei and e--e-, in/btween
molecules

Impossible to calculate total energy of

system.
Changes in energy can be determined
experimentally

 S (s) + O2 (g) SO2 (g)

Dont know E on reactant/product
Can measure accurately change in energy
content E
Reaction gives off heat. Energy product
less than reactant. E is negative
Chemical energy converted to thermal
energy

 More interested in system. More useful

equation:
E = q + w
q: heat exchange between system and
surrounding
: +ve if endothermic, -ve if exothermic
w: work done on (or by) system
: +ve: work done on system by surrounding
(compression),
-ve: work done by system on surrounding
(expansion)

Heat
Heat is not a state function, like work
Example: it takes 4148J of energy to raise
the T of 100g of water from 20oC to 30oC.
This can be gained by:
Directly as heat energy from a Bunsen burner
By doing work on the water with out adding
heat (stirring)
By a combination of the above two methods

Enthalpy
To quantify the heat flow into or out of a
system in a constant pressure process
Impossible to determine enthalpy of
substance

 Measure change in enthalpy, H

Enthalpy of reaction, H
= H (product) - H(reactant)
Endothermic: positive
Exothermic : negative

Thermochemical equations
Show enthalpy changes as well as mass
relationship
Combustion of methane
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O(l)
H= -890.4kJ

 Guidelines for writing and interpreting

thermochemical equations
Stoichiometric coefficient refer to number of
moles of substance
Reverse equation, magnitude of H same but
sign changes
Multiply equation by factor of n then H must
also change by the same factor
Must always specify the physical state

Calorimetry
Measurement of heat changes
Specific heat, s: amount required to raise
temperature of one gram of the substance
by one degree Celsius (J/g.oC)
Heat capacity, C : amount of heat required
to raise the temperature of a given
quantity of the substance by one degree
Celsius (J/oC)

 C = ms (where m is the mass)

If specific heat and amount of substance is
known change in sample temperature T
will tell us the amount of heat, q, that has
been released/ absorbed in particular
process.
q = ms T

q is positive (endothermic) and negative

for exothermic process

Example
A 466 g sample of water is heated from
8.5oC to 74.6oC. Calculate the amount of
heat and state whether heat is absorbed
or released by the water. (Specific heat of
water = 4.184 J/goC)

Constant-volume Calorimetry
Measure heat of
combustion
Isolated system
qsystem = qcal + qrxn = 0

Example
A quantity of 1.435 g of naphthalene
(C10H8) was burned in a constant volume
bomb calorimeter. Consequently, the
temperature rose from 20.28oC to
25.95oC. If the heat capacity of the bomb
plus water was 10.17 kJ/oC, calculate the
heat of combustion of naphthalene on a
molar basis (find the molar heat of
combustion)

Constant-Pressure Calorimetry
Noncombustion
reactions
Heat change for
process (qrxn) = H
Neglect the small
heat capacity of the
coffee cups in our
calculation

Standard enthalpy of formation

and reaction
Standard enthalpy of formation (Hof) :
heat change that results when one mole of
a compound is formed from its elements at
a pressure of 1 atm (standard state).
Hof of any element in its most stable form
is zero
Hof (O2) = 0 Hof (O3) 0

 From Hof values the standard enthalpy of

reaction Horxn can be calculated
Horxn :Enthalpy of reaction carried out at 1
atm
aA + bB cC + dD
Horxn = [cHof (C) + dHof (D)] [aHof (A)
+ bHof (B)]
Horxn = nHof (Product) mHof(Reactant)

Direct method of measuring Hof

Works for compounds that can be readily
synthesized from their elements
Example: enthalpy of formation of carbon
dioxide
C(graphite) + O2 (g) CO2 (g) Horxn=-393.5kJ

Indirect method measuring Hof

Many compounds cannot be directly
synthesized from their elements (proceed
too slowly/ side reactions produce other
substance than desired compound)

 Hesss law: when reactants are converted

to products, the change in enthalpy is the
same whether the reaction takes place in
one step or in a series of steps
General rule of applying:
Arrange series of chemical equation in a way
that when added together all species will
cancel except reactant and product that
appear in the overall rxn
Multiply or reverse equation

5.2 Second law of

thermodynamics

Spontaneous process and

entropy
Predict whether or not a reaction will occur
when reactants are brought together under
a special set of conditions.
Reaction that does occur under the given
set of conditions is called a spontaneous
process
Reaction that does NOT occur under
specified conditions is non-spontaneous

Entropy
Entropy: measure of randomness or
disorder of a system.
Greater disorder therefore greater entropy
Entropies of elements and compounds are
+ve
Entropy state function
S = Sf Si

Example
Predict whether the entropy change is
greater than or less than zero for each of
the following process
Freezing of ethanol
Evaporating a beaker of liquid bromine at
room temperature
Dissolving sucrose in water
Cooling nitrogen gas from 80oC to 20oC

Second law of thermodynamics

Connection of entropy and spontaneity
The entropy of the universe increases
in a spontaneous process and remains
unchanged in an equilibrium process
Universe= system + surroundings
Suniverse = Ssystem + Ssurrounding

 Second law:
- For a spontaneous process:
Suniverse = Ssystem + Ssurrounding > 0
- For an equilibrium process:
Suniverse = Ssystem + Ssurrounding = 0

Entropy changes in the system

aA + bB cC + dD
Sorxn = [cSo (C) + dSo (D)] [aSo (A)
+ bSo (B)]
Sosystem = Sorxn = nSo (Product)
mSo(Reactant)

Entropy changes in the

surrounding
Exothermic process: heat transferred to
surrounding enhance motion of molecules
in surrounding, increase disorder, increase
entropy of surrounding
Endothermic process: heat absorbed from
surrounding molecular motion decreases,
decreases entropy surrounding

Example
Determine whether the synthesis of ammonia
is spontaneous at 25oC.
N2 (g) + 3H2(g) 2NH3(g) Ho= -92.6kJ/mol

Third law of thermodynamics

The entropy of a perfect crystalline
substance is zero at absolute zero of
temperature.
The third law enables us to determine the
absolute entropies of substances

 Gibbs free energy, G

G = H TS
The energy available to do work
Is a state function
In summary:
G <0 :rxn spontaneous in forward direction
G >0 :non-spontaneous rxn. rxn
spontaneous in opposite direction
G =0 :the system is at equilibrium. No net
change

Standard free energy changes

aA + bB cC + dD
Gorxn = [cGfo (C) + dGfo (D)] [aGfo (A)
+ bGfo (B)]
Gorxn =nGfo (Product) mGfo(Reactant)
Gfo = standard free energy of formation
Free energy change that occurs when 1 mole
of the compound is synthesized from its
elements at standard states

 Standard free energy change of any

element in its stable form is zero.