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Chapter 3

Chemical
Thermodynamics

LESSON OUTCOMES
At the end of this lecture, students
should be able to:
1. Recognize and use thermodynamic
terms: system, surrounding, heat,
work, internal energy, Gibbs Free
energy, enthalpy and entropy
2. Describe the first law and second law
of thermodynamics
3. Calculate the change in internal
energy

SCOPE
Thermochemistry
Chemical
Thermodynamics

3.1
Thermochemistry
Forms of Energy and Their
Interconversion
Enthalpy: Heats of Reaction and
Chemical Change
Calorimetry: Laboratory Measurement
of Heats of Reaction
Stoichiometry of Thermochemical
Equations
Hesss Law of Heat Summation

3.1.1
Energy
Forms
of Energy
and Their
Interconversion
All changes in matter - accompany by
changes in the energy/heat content of the
matter.
e.g. 1. Snow melts - energy is absorbed
2. H2O vapor condenses to rain energy is
release
Thermodynamics: the study of heat & its
transformation.
Thermochemistry:

branch

of

3.1.1 Energy

Forms of Energy and Their


Interconversion
All energy (potential or kinetic) convertible from one to the other
An object has:
(i) potential energy by virtue of its
position
(ii) kinetic energy by virtue of its

3.1.1 Energy
The System and Its
surroundings
System must be defined - to make a
meaningful observation &
measurement of a change in energy.
System: part of universe whose
change to be observed.
Surroundings: everything relevant to
the change of the system

The 3.1.1
system Energy
and Its
Surroundings

Contents of the flask: system


Flask & the laboratory:

3.1.1 Energy

Forms of Energy and Their


Interconversion
Sum of potential and kinetic energy for all
the particles in the system = internal
energy, E
Change or difference in internal energy,
E = difference between the
systems internal energy after the change
(Efinal) and before the change (Einitial)

E = Efinal - Einitial = Eproducts


E

3.1.1 Energy

Forms of Energy and Their


Interconversion
A reacting chemical system can change its
internal energy in either of two ways by:
(i) losing some energy to surroundings:
Efinal Einitial
(ii) gaining some energy from surroundings:
Efinal > Einitial
Change in internal energy - a transfer of
energy from system to surroundings & vice

3.1.1
Energy
flow Energy
to and from
a system

Energy diagrams for the transfer of internal


energy (E) between a system and its
surroundings

Energy
Heat and3.1.1
Work: Two
Forms of
Energy Transfer
Energy transfer outward from the system or
inward from the surroundings can appear in
two forms; heat & work
Heat, q (or thermal energy)
energy transferred between a system and
its surroundings
as a result of a difference in temperatures
between the system and surroundings
Work, w
energy transferred when an object is moved

3.1.1
Energy
Heat and
Work: Two
Forms of
Energy Transfer
Total change in a systems internal energy:

E = q + w
q & w can be either +ve/-ve:
energy into the system: +ve
energy out from the system: -ve

3.1.1 Energy

Example of energy transfer as heat


only
A system that does no work but transfers
energy as heat (q), work, w = 0. E = q

3.1.1 Energy
Example of energy transfer as heat
only

Hot water in a beaker - heat out from a


system
System: hot water
q = -ve as heat was lost by the system.

E = -ve
Ice water in a beaker - Heat into a
system
System: ice water
q = +ve as heat was gained by the

3.1.1 Energy
Example of energy transfer as work only
Heat , q = 0. E = w

3.1.1 Energy
Example of energy transfer as work only
Work done by a system
Reaction between Zn & HCl in an insulated
container attached to a piston-cylinder assembly
System: atoms making up the substances
Zn (s) + 2H+ (aq) H2(g) + Zn2+ (aq) + 2Cl-(aq)
As the H2 gas forms, the system used some of the
internal energy on the surroundings and push the
piston outward.
Energy is lost by the system as work, w = -ve,

E = -ve

3.1.1 Energy
q = +ve : system gains heat
q = -ve: system loses energy
w = +ve: work done on system
w = -ve: work done by system

3.1.1 Energy
The Law of Energy Conservation /
The First Law of Thermodynamics
Energy
can be converted from one to another
cannot simply appear or disappear
cannot be created or destroyed
First Law of Thermodynamics: The total energy
of the universe is constant

3.1.1 Energy
The Law of Energy Conservation /
The First Law of Thermodynamics
Energy of the system + energy of the
surroundings remains constant: energy is
conserved.
A mathematical expression of the first law of
thermodynamics

Euniverse = Esystem + Esurroundings = 0

3.1.1 Energy
Units of Energy

SI unit = Joule (J)

1 cal (non SI unit) = 4.184 J


Heat, work, potential energy, kinetic energy
are expressed in Joules
In the case of work:
Work, w = Force (F) x distance (d)
where F = mass (m) x acceleration (a) in units
kgm
of
2
s
kgm
kgm2
w = s2 x m s2 J

Example
When gasoline burns in a car engine, the heat
released causes the products CO2 and H2O
expand, which pushes the pistons outward.
Excess heat is removed by the cars cooling
system.

If the expanding gases do 451 J of

work on the pistons and the system loses 325


J to the surroundings as heat, calculate the
change in energy (E) in J, kJ and kcal.

Solution

Plan: Define the system and surroundings


System - reactants and products
Surroundings - pistons, cooling system & rest

of the car
Heat released by the system, q = -ve, work

done by the system to push the piston


outward, w = -ve
Calculating E in J:
q = -325 J, w = -451 J,

3.1.1
Energy
State Functions and the Path
Independence of the Energy
Change
Systems internal energy, E - state of
function
property determined by the current state of
the system
not dependent on the path the system took
to reach the state
Changes in state function (such as E, P,
V) depend only on the initial and final
states of the system

3.1.1
Energy
State Functions and the Path
Independence of the Energy
Change
Heat, q and work, w are not state function
their values depend on the path the
system takes in undergoing the energy
change
Note: Symbols for state functions (such as
E,P,V) are capitalized

3.1.2 Enthalpy
Enthalpy is a thermodynamic property of a
system.
Enthalpy is defined by H = E + PV
Thus, change in enthalpy, H = E + P V
(eq. 1)
Total change in a systems internal energy
under conditions of constant pressure,

E = qp + w

(eq. 2)

3.1.2 Enthalpy
In Chemistry, we are most often concern with
the reactions/systems that occur in solution
under conditions of constant atmospheric
pressure. Hence the system is free to expand
or contract and this means that it potentially
do work. Thus work done by the system, w =
P V (eq. 4)
Substituting eq. 4 in eq. 3,
H = qp (eq. 5)
Thus, the heat of reaction at constant
pressure is equal to H (change in

3.1.2 Enthalpy
Comparing E and H
For many reactions, H is equal / very close to E.
Three cases:
(i) Reactions that do not involve gases
e.g. 2KOH(aq) + H2SO4(aq) K2SO4(aq) +
2H2O(l)
Liquids & solids undergo very small volume
changes,

3.1.2 Enthalpy
Comparing E and H
(ii) Reactions in which the amount (mol) of gas
does not change. Total amount of gaseous
reactants = total amount of gaseous products
e.g. N2(g) + O2(g) 2NO(g), V = 0, PV = 0,

H E
(iii) Reactions in which the amount (mol) of gas
does change. PV 0, qp is usually much
larger than PV
From eq. 1, H = E + PV, H = qp = E +
P V

3.1.2 Enthalpy

Exothermic and Endothermic


Processes
Enthalpy is a state function
The enthalpy change of reaction, H, is
also called the heat of reaction, Hrxn.

H = Hfinal - Hinitial = Hproducts


Hreactants

3.1.2
Enthalpy
Exothermic and Endothermic
Processes
An exothermic (heat out)
process releases heat
results in a decrease in the enthalphy
Exothermic: Hfinal Hinitial, H 0/-ve
An endothermic (heat in)
process absorbs heat
results in an increase in the
enthalphy

Example
In each of the following cases, determine the
sign of H, state whether the reaction is
exothermic or endothermic
(a) H2(g) + 1/2 O2(g) H2O(l) + 285.8 kJ
(b) 40.7 kJ + H2O(l) H2O(g)

Solution
(a) Heat is a product (on the right), so

and

H 0

the reaction is exothermic

(b) Heat is a reactant (on the left), so H 0


and the reaction is endothermic

Enthalpy
Some 3.1.2
Important
Types of
Enthalpy Change
(i) Heat of combustion (Hcomb): when 1
mole of substance reacts with O2 in
a combustion reaction
e.g. C4H10(l) + 13/2 O2(g) 4CO2(g) + 5H2O, H =
Hcomb

(ii) Heat of formation (Hf): when 1 mole


of compound is produced from its
element

3.1.2
Enthalpy
Some Important Types of
Enthalpy Change
(iii)Heat of fusion (Hfus): when 1 mole
of a substance melts
e.g. NaCl(s) NaCl(l), H = Hfus
(iv)Heat of vaporization (Hvap): when 1
mole of substance vaporize

3.1.3 Calorimetry
Measurement
of Heats of
Reaction
Enthalpy of a system in a given state

- cannot be measured
Change in enthalpy - can be measured

Heat Capacity & Specific Heat


Capacity
Quantity of heat (q) absorbed by an

object is proportional to its


temperature change

3.1.3 Calorimetry
Measurement
of Heats of
Reaction
Heat Capacity & Specific Heat
Capacity
Heat capacity, C = q/ T = quantity of

heat required to change the


temperature of substance by 1K. (Unit:
J/K)

T =
quantity of heat required to change the
temperature of 1 gram of a substance
by 1K (Unit: J/g.K).

Specific heat capacity, c = q/m

Example

A welded layer of copper on the bottom of a


skillet weighs 125 g. How much heat is
needed to raise the temperature of the
copper layer from 25oC to 300oC?. The
specific heat capacity (c) of Cu is 0.387 J/gK.

Solution
T = Tfinal - Tinitial = 300oC 25oC = 275oC =
275 K
q = c x mass(g) x T = 0.387 J/gK x 125 g x

3.1.3 Calorimetry

The Practice of Calorimetry


Calorimeter an equipment used to measure
the heat released/absorbed by a physical or
chemical process. Two common types:
constant-pressure & constant-volume
calorimeters
Constant-Pressure Calorimetry
A coffee/styroform-cup calorimeter
Use to measure the heat (qp) of many
processes that are open to the laboratory
atmosphere

3.1.3 Calorimetry
Constant-Pressure
Calorimetry

A coffee-cup

calorimeter
Process:
solid (system) is
weighed, heated to
some known
temperature, added to
a sample of water
(surroundings) of
known temperature &
mass in the calorimeter

3.1.3 Calorimetry
A coffee-cup
calorimeter
Continual
stirring which distribute the
released heat
Final water temperature (final temperature of

the solid) is measured


Heat lost by the system (-q) is equal in
magnitude but opposite in sign to the heat
gained (+q) by the surroundings:
qsolid = qH2O
(csolid x masssolid x Tsolid) = cH20 x massH20 x
T

Example
A 25.64 g sample of solid was heated in a test
tube to 100.00oC in boiling water and carefully
added to a coffee-cup calorimeter containing
50.00 g water. The water temperature
increased from 25.10oC to 28.49oC. What is the
specific heat capacity of the solid? (Assume all
the heat is gained by the water)

Solution

J calculate c
Plan -summarize the information
given,
solidK
4.184
x 50.00 g x 3.93
c H 2 O x mass H 2O x TH 2O
gK
c solid =
=
masssolid x Tsolid
25.64 g x ( 71.51 K)
J
= 0.387
gK

3.1.3 Calorimetry
Constant-Volume Calorimetry
Common type: bomb

calorimeter
Use to measure very
precisely the heat
released in
combustion reaction
Knowing mass of the
sample and the heat
capacity of the
calorimeter, the
measured T is used
to calculate the heat
released

Example
A manufacturer claims that its new
dietetic dessert has fewer than 10
Calories per serving. To test the
claim, a chemist at the Department
of Consumers Affairs places one
serving in a bomb calorimeter and
burns it in O2. The temperature
increases 4.9370C. Is the
manufacturers claim correct?

Solution
When the dessert burns, the heat
released is gained by the
calorimeter:
-qsample = qcalorimeter
Heat is found by mutiplying the heat
capacity of the calorimeter by T
qcalorimeter = heat capacity x
T
= 8.151 J/k x
4.937 K

3.1.4 Stoichiometry of Thermochemical Equations

Thermochemical equations
a balanced equation that states the
heat of reaction (Hrxn)
Note: Hrxn value refers to the
enthalpy change for the amounts of
substances in that specific reaction

3.1.4 Stoichiometry of Thermochemical Equations

Two aspects of enthalpy change:


(i) Sign: Sign of H depends on the reaction
of the change
Sign of a forward reaction is opposite
that of the reverse reaction
e.g. Decomposition of 2 mol water
(endothermic):
2H2O(l) 2H2(g) + O2(g)
Hrxn = 572
kJ
Formation of 2 mol water (exothermic):
2H2(g) + O2(g) 2H2O(l)
Hrxn =

3.1.4 Stoichiometry of Thermochemical Equations

(ii) Magnitude
Magnitude of H is proportional to the
amount of substances in the reaction
e.g. Formation of 1 mol water:
H2(g) + 1/2 02(g) H2O(l) Hrxn =
-286 kJ
Formation of 2 mol water
2H2(g) + O2(g) 2H2O
Hrxn =
-576 kJ

3.1.5 Hesss Law of Heat


Summation
Hesss law of heat summation: the
enthalpy change of an overall process is
the sum of the enthalpy changes of its
individual steps
Hesss Law - the difference between the
enthalpies of the reactant and the
product has the same value even though
the reaction takes place differently

3.1.5 Hesss Law of Heat


Summation
Calculating an unknown H involves three steps:
(i)

identify the target equation, note the number of


moles of reactants and products.

(ii) manipulate the equations of known H - the target


numbers of moles of reactants and products are on
the correct sides
change the sign of H when reverse an
equation
multiply number of moles and H by the same
factor
(iii)

Add the manipulated equations to obtain the


target equation. (cancel terms that appear on both

Example
Application of Hesss Law:
Oxidation of sulfur trioxide
eq. 1: S(s) + O2(g) SO2(g)
-296.8 kJ

H1 =

eq. 2: 2SO2(g) + O2(g) 2SO3(g) H2 =


-198.4 kJ
eq. 3: S(s) + 3/2 O2(g) SO3(g)

H3 = ?

Solution
Manipulate eq.1 and/or 2 so that they add up
to eq.3
identify eq. 3 as a target, carefully note the
number of moles of reactants and products

Solution
(cont.)
Eq. 2 has twice as much SO3 as eq.3, so multiply
it by 1/2, multiply H2 by 1/2 as well

Add eq. 1 to the halved eq. 2, cancel terms that


appear on both sides:
H1 =

Eq. 1: S(s) + O2(g) SO2(g)


-296.8 kJ
1/2(Eq. 2):SO2(g) + 1/2O2(g) SO3(g)

1/2(H2) =

-99.2 kJ
Eq. 3:

S(s) + O2(g) + SO2(g) + 1/2 O2(g) SO2(g) +

SO3(g)
S(s) + 3/2O2(g) SO3(g)

3.1.5 Hesss Law of Heat


Summation
Standard Heats of Reaction
( H0rxn)

Standard states (a set of specified conditions


and concentration) are used to compare heats
of reaction and other thermodynamic data:
(i) Gas: standard state - 1 atm
(ii) Substance in aqueous solution:
standard state - 1 M
(iii) Pure substance (element or compound):
standard state: usually the most standard at
1 atm and the temperature of interest (250C)

3.1.5 Hesss Law of Heat


Summation
Standard Heats of Reaction
( H0rxn)
A right superscript zero indicates when
thermodynamics variable has been
determined with all substances in their
standard states.
e.g. Standard heat reaction, H0rxn, is the
H0rxn measured with all substances in
their standard states.

3.1.5 Hesss Law of Heat


Summation
Formation Equations and Their Standard
Enthalpy

In a formation equation, 1 mol of compound


forms from its elements
Standard heat of formation (H0f) - enthalpy
change accompanying the formation
equation when all the substances are in their
standard states.
e.g.
C(graphite) + 2H2O(g) CH4(g)
-74.9 kJ

H0f =

Exampl
e

Write balanced equations for the formation of 1 mole of the


following compounds from their elements in their standard
states and include H0f
(i) Silver chloride, AgCl, a solid at standard conditions
(ii)

Calcium carbonate, CaCO3, a solid at standard conditions

(iii)

Hydrogen cyanide, HCN, a gas at standard conditions

Solution
(i) Ag(s) + 1/2 Cl2(g) AgCl(s)

H0f = -127.0 kJ

(ii) Ca(s) + C(graphite) + 3/2 O2(g) CaCO3 H0f = -1206.9 kJ


(iii) 1/2 H2(g) + C(graphite) + 1/2 N2(g) HCN

H0f = 135 kJ

3.1.5 Hesss Law of Heat


Summation
Determining H0rxn from H0f
values of Reactants and
Products
By applying Hesss Law,

H0f values can be used to

determine H0rxn for any reaction:

H0rxn = m H0f (products) - n H0f


(reactants)
m & n = no of moles

Suppose we want H0rxn for:


0
TiO{(s)
4HCl(g) 0
H0rxn = {H0fTiCl
[TiO42(l)
(s)]++2H
4H
H0+
2O(g)
f [HCl(g)]} - 2
f [TiCl4(l) + 2H f
H2O(g)]}

e
Nitric acid, with an annual production of about 8 billion
kg, is used to make many products, including fertilizer,
dyes and explosive. The first step in its industrial
production is the oxidation of ammonia: 4NH3(g) +
5O2(g) 4NO(g) + 6H2O(g)
Calculate H0rxn from H0f values

Solution
H0rxn = mH0f (products) - nH0f (reactants)
= {4H0f [NO(g)] + 6H0f [H2O(g)]} - {4H0f
[NH3(g)] +
5H0f
[O2(g)]}

3.2 Chemical
Thermodynamics
Spontaneous Processes
Entropy
Molecular Interpretation of Entropy
Calculation of Entropy Changes
Second Law of Thermodynamics
Entropy Change for a Phase Transition
Gibbs Free Energy
Free Energy and Temperature
Free Energy and the Equilibrium Constant

3.2 Chemical
Thermodynamics
Area of chemistry that explores energy
relationship
Limitations of First Law of
Thermodynamics
only tells the amount of heat
released/work done by the system & the
amount of heat gained/work done on the
system
sign of H - not enough to predict
whether the reaction will proceed

3.2 Chemical
Thermodynamics
Reactants or products favoured In
addition to H, change in randomness
or disorder in chemical reaction is
considered
New aspect in discussion of
thermodynamics spontaneous
process
related to disorder in chemical

3.2.1 Spontaneous
Process
Spontaneous process: Chemical or
physical change occurs by itself
requires no continuing outside agency
/ occurs without any outside
intervention
A rock at the top of a hill
rolls down by itself - occur
spontaneously /
naturally
rolls up - not natural process /

3.2.1 Spontaneous
Process
Temperature: have an impact on the
spontaneity
e.g. endothermic process of melting ice,
at T 00C:
ice melts spontaneously (ice liquid water)
reverse process (liquid water ice),
nonspontaneous
But at T 00C:
liquid water converts into ice spontaneously

3.2.2 Entropy
Entropy, S
a thermodynamic quantity - a measure of
the randomness/disorder of a system.
SI unit: Joules per Kelvin (J/K)
a state function
quantity of S depends only on variables
(such as T & P) that determine the state of
substance

3.2.2
Entropy
Randomness/disorder of
the system
(i) Solids: have much more regular structure
than liquids.
Liquids > disordered than solids
(ii) Particles in a gaseous state are in random
motion.
Gases > disordered than liquids
(iii)Any process that increases the amount of
particles,

3.2.2
Entropy
Randomness/disorder of
the system
Consider the melting of ice:
Ice: an ordered crystalline structure
Ice melts liquid, crystalline structure
breaks down, resultant a less ordered
liquid structure
In ice, H2O molecules occupy regular, fixed
positions; ice has a relatively low S
In liquid water, molecules moves about
freely, disordered structure; liquid water has
greater entropy than ice

3.2.2
Entropy
Randomness/disorder of
the system
Entropy change, S

S = Sfinal Sinitial
S of a system to the disorder of the system
Ssystem 0,
implies the system becomes more
disordered
Ssystem 0,

3.2.3 Molecular Interpretation


of Entropy
Structure & behaviour of molecules - affect the
entropy of the system
e.g. Entropy of the system increase (S > 0)
when:
(i) gas molecules spread out in a larger
volume
(ii) phase changes: solid liquid, liquid
gas
e.g. Entropy of the system decrease (S < 0)
when:
(i) condensing a gas,
(ii) freezing a liquid

3.2.3 Molecular Interpretation


of Entropy
e.g. 2NO(g) + O2(g) 2NO2(g)
Entropy change = -ve because 3 molecules

of gas react to form 2 molecules of gas


Formation of new N-O imposes more order,

atoms are more tied up in the products


than in the reactants

Leads to a decrease in the entropy

3.2.3 Molecular Interpretation


of Entropy
Formation of the new bonds - decreases the
number of degrees of freedom/forms of
motion atoms are less free to move in
random fashion
In general - the greater the no. of freedom
of system, the greater its entropy
The degrees of freedom of molecules associate with three types of motion for the
molecule:
(i)
Translational motion
(ii) Vibrational motion

Molecular Interpretation of
Entropy
In general - entropy increasing with increasing
temperature.
Entropy of the phases of a substance:

Ssolid < Sliquid < Sgas


In general, the entropy is expected to
increase when:
(i)
Liquids or solutions are formed from
solids
(ii) Gases are formed from either solids or

3.2.4 Calculation of Entropy


Change
Standard molar entropies, S0 - molar entropy

values of substances in their standard states


Entropy change in a chemical reaction, S0:

S = mS

products - n S reactants
o

= sum of
m = amounts (mol) of the products
n = amounts (mol) of the reactants

Example
Calculate S0 for the synthesis of ammonia
from N2(g) and H2(g):
N2(g) + 3H2(g) 2NH3(g)

Solution
S0 = 2S0(NH3) - [S0(N2) + 3S0(H2)]
Substituting the appropriate S0 values
J
J
J

S 2 mol 1925
1mol 191.5
3 mol 130.6

molK
molK
molK

J
-198.3
K

Example
Choose the substance that has greater entropy in
each pair, and explain your choice:
(a) 1 mol of NaCl(s) or 1 mol of HCl(g) at 250C
(b) 2 mol of HCl(g) or 1 mol of HCl(g) at 250C
(c) 1 mol of N2(s) at 24 K or 1 mol of N2(g) at 298 K

Solution
(d) Gaseous HCl has the higher entropy because

gases are more disordered than solids


(e) The sample containing 2 mol of HCl has twice the
entropy of the sample containing 1 mol
(f) The gaseous N2 sample has the higher entropy
because gases are more disordered than solids

3.2.5 Second Law of


Thermodynamics
Second Law of Thermodynamics: total
energy of a system and its surroundings
always increases for a spontaneous
process
Note: the difference between the entropy
& energy
energy - cannot be created or destroyed
during chemical change
entropy-created during a spontaneous or
natural process

3.2.5 Second Law of


Thermodynamics
For a spontaneous process carried out at
a given temp.
The second law can be restated in a
form that refers only to the system
Consider the changes in entropy that
occur in the system
- Process takes place entropy is
created, at the same time heat flows
into/out of the system
- Entropy accompanies that heat flow
When heat flow into the system
entropy flows into the system

3.2.5 Second Law of


Thermodynamics
The change in entropy, S, of the system at
a given temperature:

q
S entropycreated
T

quantity of entropy created during


spontaneous process cannot be directly
measured
quantity of entropy created = +ve, by
deleting it from the right side of

3.2.5 Second Law of


Thermodynamics
The restatement of the second
law
For a spontaneous process at a given
temperature, the change in entropy of

q
the system is greater than the heat
T

divided by the absolute temperature,

3.2.6 Entropy Change for a


Phase Transition
Certain processes occur closely at
equilibrium.
Under equilibrium conditions, no significant
amount of entropy is created. The S results
only from the absorption of heat.
Thus, entropy change for a phase change:

q
S
T
equilibrium
process

Examples of phase changes under


equilibrium:

Example
The heat vaporization, Hvap, of carbon
tetrachloride, CCl4, at 250C is 43.0 kJ/mol.
CCl4(l) CCl4(g)

Hvap = 43.0

kJ/mol
If 1 mol of liquid CCl4 at 250C has an entropy of
214 J/K, what is the entropy of 1 mol of the
vapor in equilibrium with the liquid at this
temperature?

Solution
1 mol of CCl4 increases in entropy by 144 J/K
when it vaporizes. Thus, entropy of 1 mol of
vapor = entropy of 1 mol of liquid (214 J/K) +
144 J/K = 358 J/mol.K

Hvap
S =
T

J
43.010
J
mol
=
=144
298K
molK
3

Energy
X J Willard Gibbs (1839 -1903) proposed a way to use H & S to
predict whether a given reaction will be
spontaneous
Gibbs proposed a new state function
Gibbs free energy (or just free energy)
Gibbs free energy, G = H - TS, T =
absolute temp.
At constant T, the change in free energy
of the system, G = H - TS

3.2.7 Gibbs Free


Energy
If T & P are constant, the relationship
between the sign of G and the
spontaneity of a reaction:

G = -ve, reaction is spontaneous in


the forward reaction

(i) If

G = +ve,
reaction in the forward reaction is
non spontaneous, work must be
supplied from the surroundings to
make it occur
reverse reaction will be spontaneous

(ii) If

3.2.7 Gibbs Free


Energy

Standard Free Energy


Change
Standard free energies of formation, Gof

,are useful in calculating the standard free


energy change for chemical process
o
G f

o
G f (products)

o
G f (reactants )

= sum of,
m = amounts (mol) of products
n = amounts (mol) of reactants

3.2.7 Gibbs Free


Energy Free Energy
Standard
Change
G0 tells whether a mixture of
reactants and products (under standard
conditions):

Quantity of

(i) would spontaneously react in the forward

direction to produce more products G0


<0

(ii) or in the reverse direction to form more

reactants G0 > 0

Example
(a) Calculate the standard free-energy change for

the following reaction at 298 K:


N2(g) + 3H2(g) 2NH3(g)
(b) What is

reaction?

G0 for the reverse of the above

G o 2 molG fo NH3 1molG fo N2 3 molGfo H2


Solution

(a)

kJ
kJ
kJ

2 mol -16.66

1
mol
0

3
mol
0

mol

mol
mol

- 33.32kJ

(b) 2NH3(g) N2(g) + 3H2(g), G0 = +33.32 kJ

3.2.8 Free Energy and


Temperature
Consider equation :

G = H (enthalpy term) - T S
(entropy term)
Generally H & S change very little with
T. However, the value of T directly affects
the magnitude of -TS
As T increases, the magnitude of the term
-TS increases. It will become relatively
more important in determining the sign &

3.2.8 Free Energy and


Temperature
Example: melting of ice liquid water (P = 1 atm)
H2O(s) H2O(l), H > 0, S > 0
endothermic process, H = +ve
entropy increases during process, S = +ve, -TS =
-ve
At T < 00C, magnitude of H > magnitude of S
+ve enthalpy term dominates, leading to a +ve
value of G.
Melting of ice is not spontaneous at T < 00C,
reverse process (liquid water to ice) is spontaneous
at T < 00C
When T > 00C, magnitude of -TS > magnitude of H

3.2.8 Free Energy and


Temperature
Example: melting of ice liquid water (P = 1 atm)
H2O(s) H2O(l), H > 0, S > 0
endothermic process, H = +ve
entropy increases during process, S = +ve, -TS
= -ve
At normal melting point of water, T = 00C, & the
two phases are in equilibrium.
At T = 0, H & -TS are equal in magnitude. G
=0
Under standard conditions (at 250C)

Example
The Haber process for the production of
ammonia involves the following equilibrium:
N2(g) + 3H2(g) 2NH3(g)
Assume that H0 and S0 for this reaction do
not change with temperature
(a) Predict the direction in which G0 for this

reaction changes with increasing


temperature
(b) Calculate G0 for the reaction at 500oC

Solution
G0 become less negative (or more

positive) with increasing temperature.


Thus the driving force for the production
of NH3 becomes smaller with increasing
temperature
G0 = H0 - T S0

o 500 + 273 = 773 K


T
=
G 92.38kJ - 773K - 198.3

- 92.38kJ 153kJ
61kJ

1kJ

3
K 10 kJ

3.2.8 Free Energy and the


Equilibrium Constant
Another two ways to use free energy as a
powerful tool in analysis of chemical
reaction
(i) How to use G0 value to calculate the

value of
conditions

under

non-standard

(ii) How to directly relate the G0 for a

3.2.8 Free Energy and the


Equilibrium Constant
Most chemical reactions occur under non-

standard conditions
Free-energy change under any other
conditions:

G = G0 + RT ln Q
R = ideal gas-constant, 8.314 J/mol-K
T = absolute temperature
Q = reaction quotient that corresponds to the
particular reaction mixture of interest

3.2.8 Free Energy and the


Equilibrium Constant
Note: Suppose the general equilibrium

equation:
aA + bB pP + qQ
a, b, p & q = coefficients in balanced
chemical
p
q
equation (RECALL
CHEMISTRY
[ P] Q
I)equilibrium constant , K =

[ ]

[ A] [ B]
a

3.2.8 Free Energy and the


Equilibrium Constant
Q is calculated by substituting reactant and
product concentrations in the equilibriumconstant expression
Under standard conditions: [reactants] &
[products] = 1
Q = 1, ln Q = 0, G = G0
At equilibrium:
G = 0, Q = K
G = G0 + RT ln Q
0

G
K exp
RT

The End