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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 and second law of
thermodynamics
3. Calculate the change in internal
energy

SCOPE
Thermochemistry
Chemical
Thermodynamics

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
Standard Heats of Reaction

3.1 Thermochemistry
All changes in matter - accompany by changes in

the energy/heat content of the matter.


1. Snow melts energy
is
absorbed
2.
H2 O
vapor
condenses
to
rain - energy is
release

Thermodynamics:
the
study
of
heat
&
its
transformation.
Thermochemistry: branch of thermodynamics, deals

Energy
Forms of Energy and Their Inter
conversion
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 motion

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 System and Its


Surroundings
System refers to the particular chemical

species being studied


Surroundings are everything else
Universe refers to the system and the
surroundings
Boundary defined as region across which heat
flows

The system and Its Surroundings

Contents of the flask: system


Flask & the laboratory: surroundings

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
Ereactants

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 versa

Energy Flow to and from a


System

Energy diagrams for the transfer of internal

energy (E) between a system and its


surroundings

Heat and 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 by a force

Heat and Work:


Two Forms of Energy Transfer
Total change in a systems internal

energy:

E = q + w

(1)

q & w can be either +ve/-ve:


energy into the system: +ve
energy out from the system: -ve

Examples of energy transfer as heat only


A system that does no work but transfers energy

as heat (q), work, w = 0. E = q

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 system.


E = +ve

Example of energy transfer as work only


Heat , q = 0. E = w

Work done on
system
E = +ve

Push piston down - Work done on a system


If the external pressure on the piston is increased, the

work is done on the system by the surroundings.


System gains energy, w = +ve, E = +ve

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) + 2HCl (aq) H2(g) + Zn2+ (aq) + 2Cl(aq)
As the H2 gas forms, the system used some of its
internal energy on the surroundings and push the
piston outward.
Energy is lost by the system as work, w = -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:
kgm
Work, w = Force (F) x distance (d)
2
s
where F = mass (m) x acceleration (a) in units of
2
kg
m
kg
m
w =
x m
J
2
2
s
s

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
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,
E
=q+w
= -325 J + (-451J) = -776 J = -0.78 kJ
= -185.47 cal = 0.19 kcal
(1cal = 4.184
J)

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

E, P, V)
depend only on the initial and final states of the
system

Changes in state function (such as

State Functions and the Path


Independence of the Energy Change
E (sum of q and w) is
constant, even though the specific values of q and
w can vary

For a given 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
Enthalphy is a thermodynamic property of a
system.
Enthalpy is defined by H = E + PV
Thus, change in enthalphy, 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,
V 0, PV 0, H E

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 +
PV

3.1.2 Enthalpy
Exothermic and Endothermic
Processes
Enthalphy is a state function
The enthalphy 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
Endothermic: Hfinal Hinitial, H 0/+ve

Example 1
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 H 0 and
the reaction is exothermic
(b) Heat is a reactant (on the left), so H 0 and the
reaction is endothermic

Some 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
compound is produced from its element
e.g. K(s) + 1/2 Br2 (l) KBr(s), H = Hf

of

(iii)Heat of fusion (Hfus): when 1 mole of a


substance melts
e.g. NaCl(s) NaCl(l), H = Hfus

Calorimetry: Measurement of Heats


of Reaction
Enthalphy of a system in a given state - cannot be

measured

Change in enthalphy - can be measured

Specific Heat Capacity


Quantity of heat (q) absorbed by an object is

proportional to its temperature change

T or q = constant x T or q/T = constant

Calorimetry: Measurement of Heats


of Reaction
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

Heat absorbed or released, q = c x mass x T

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
250C to 3000C?
The specific heat capacity (c) of Cu is
0.387 J/gK.

Solution
T = Tfinal - Tinitial = 3000C - 250C = 2750C =
275 K
q = c x mass (g) x T
= 0.387 J/gK x 125 g x 275 K
= 1.33 x 104 J

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
Common use - to determine the specific heat
capacity of a solid (does not react/dissolve in
water)

Process:
solid (system) is

weighed, heated
to some known
temperature,
added to a
sample of water
(surroundings) of
known
temperature &
mass in the
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, substituting in equation
-(csolid x masssolid x

Tsolid) = cH20 x massH20 x TH20

All the quantities are known except csolid

Example
A 25.64 g sample of solid was heated in a
test tube to 100.000C in boiling water
and carefully added to a coffee-cup
calorimeter containing 50.00 g water.
The water temperature increased from
25.100C to 28.490C. What is the specific
heat capacity of the solid? (Assume all
the heat is gained by the water)
Solution
Plan -summarize the information
given.

J
4.184 x 50.00 g x 3.39 K
c H 2O x mass H 2O x TH 2O
gK
csolid

masssolid x Tsolid
25.64 g x (71.51 K)
J
0.387
gK

Constant-Volume Calorimetry
Common type: bomb

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

Example 4
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
by 4.9370C. Is the manufacturers claim
correct? (Heat capacity of the calorimeter
= 8.151 J/K)

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
= 40.24 J = 9.62
cal

Stoichiometry of Thermochemical Equations


Thermochemical equations
a balanced equation that states the heat of reaction

(Hrxn)
Note: Hrxn value refers to the enthalphy change for
the amounts of substances in that specific reaction

Two aspects of enthalphy 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

(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) H20(l)
Hrxn =
-286 kJ
Formation of 2 mol water
2H2(g) + O2(g) 2H2O
-572 kJ

Hrxn =

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
Hess Laws - the difference between the

enthalpies of the reactant and the product has


the same value even though the reaction takes
place differently

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 reversing 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 sides of equations). Add their H

Example 5
Application of Hesss Law:

Oxidation of sulfur to sulfur trioxide


Eq. 1: S(s) + O2(g) SO2(g)
H1 = -296.8
kJ
Eq. 2: 2SO2(g) + O2(g) 2SO3(g) H2 = -198.4
kJ
Eq. 3: S(s) + 3/2 O2(g) SO3(g)
H3 = ?

Manipulate equation 1 and/or 2 so that they add up

to equation 3
identify eq. 3 as a target, carefully note the
number of moles of reactants and products
eq. 1 and 3 contain the same amount of S, so
leave eq. 1 unchanged

Eq. 2 has twice as much SO3 as Equation 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:

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


-296.8 kJ

H1 =

1/2(Eq. 2): SO2(g) + 1/2 O2(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) + 3/2 O2(g) SO3(g)
H3 = H1 + 1/2 (H2)
= -296.8 kJ + (-99.2 kJ)

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) + 2H2(g) CH4(g)


kJ

H0f = -74.9

Example 6
Write balanced equations for the formation of 1 mole of the
following compounds from their elements in their standard states
and include H0f (To obtain values, refer to Table 6.5 - page 244,
Chemistry: the molecular nature of matter and change, 2nd Edition,
Silberberg)
(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 = -127.1 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 (g) H0f = 135.1 kJ

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)

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.

Determining H0rxn from H0f


values of Reactants and
Products
H0f values can be used to
determine H0rxn for any reaction:

By applying Hesss Law,

H0rxn = nH0f (products) - mH0f (reactants)


Suppose we want H0rxn for:
TiCl4(l) + 2H2O(g) TiO2(s) + 4HCl(g)
H0rxn = {H0f [TiO2(s)] + 4H0f [HCl(g)]} - {H0f [TiCl4(l) + 2H0f
H2O(g)]}

(Products)

(Reactants)

Example 7
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) - mH0f
(reactants)
= {4H0f [NO(g)] + 6H0f [H2O(g)]}
{4H0f [NH3(g)] + 5H0f [O2(g)]}
= [4 mol (90. 3 kJ/mol) + 6 mol (-241.8
kJ/mol)]
[4 mol (-45.9 kJ/mol) + 5 mol (0 kJ/mol)]
= 361 kJ - 1451 kJ + 184 kJ - 0 kJ

Thermodynamics Chapter Outline


Spontaneous Processes
Entropy and the Second Law of

Thermodynamics
The Molecular Interpretation of Entropy
Calculation of Entropy Changes
Gibbs Free Energy
Free Energy and Temperature
Free Energy and the Equilibrium Constant

Chemical
Thermodynamics
Area of chemistry that explores energy

relationship

Limitations of First Law Thermodynamics


only tells the amount of heat released/work

done by the system & the amount of heat


gained/work done on the system

H - not enough to predict whether the


reaction will proceed

sign of

H - not the only factor governs reactants or

products favoured

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 reaction

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 / non
spontaneous: require work

Spontaneous Process
Temperature: have an impact on the

spontaneity
e.g. endothermic process of melting ice, at T
00C:
ice melts spontaneously
reverse process (liquid water ice), nonspontaneous
But at T 00C:

liquid water converts into ice spontaneously


conversion of ice liquid water, non
spontaneous

Entropy & the Second Law of


Thermodynamics
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
(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,
disorder

Consider the melting 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

Entropy change,

S = Sfinal Sinitial

S of a system to the disorder of the system


Ssystem 0, implies the system becomes more

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
A reaction leads to a decrease in the number of

gaseous molecules
generally leads to a decrease in entropy

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

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
(iii) Rotational motion

Molecular Interpretation of
Entropy
In general - entropy increases 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
liquids
(iii) No. of molecules of gas increases during
a
chemical reaction

Calculation of Entropy
Change
Standard molar entropies, S0 - molar entropy

values of substances in their standard states


Entropy change in a chemical reaction, S0:

So = nSo products - m So reactants

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

Example 8
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 9
Choose the substance that has greater entropy in
each pair, and explain your choice:
(a) 1 mol of HCl(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

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

Second Law of
Thermodynamics
For a spontaneous process carried out at
a given temperature
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
oprocess takes place entropy is
created, at the same time heat flows
into/out of the system
oentropy accompanies that heat flow
When heat flow into the system entropy
flows into the system

Second Law of
Thermodynamics
The change in entropy,

temperature:

S, of the system at a given

S entropycreated

q
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 equation:
S > q/T for a spontaneous process

Second Law of
Thermodynamics
The restatement of the second law: for a

spontaneous process at a given temperature,


the change in entropy of the system is greater
than the heat divided by the absoluteq
temperature,
T

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, the change in entropy:

q
(equilibrium
process, Eq.1)
S
T

Examples of phase changes under equilibrium:


vaporization of a liquid
fusion of a solid

Entropy Change for a Phase


Transition
Eq.1 - can be used to obtain the entropy change for

a phase change
e.g. Consider the melting of ice, Hfus 6.0 kJ (1 mol
of ice)
heat absorbed q
= heat of fusion, Hfus

S =

T
Hfus
S=
T

entropy change ,

Example 10
The heat vaporization, Hvap, of carbon tetrachloride,
CCl4, at 250C is 43.0 kJ/mol.

kJ/mol

CCl4(l) CCl4(g);

Hvap = 43.0

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

S =

H vap
T

J
43.0 10
J
mol
=
= 144
298 K
mol K
3

1 mol of CCl4 increases in entropy by 144


J/K when it vaporizes.
Thus, entropy of 1 mol of CCl4 at
equilibrium
= (214 J/K) + 144 J/K
= 358 J/mol.K

How thermodynamics is applied to the question


of whether a reaction is spontaneous?
Example:
assume a reaction occurs at constant T and P:
2NH3(g) + CO2(g) NH2CONH2(aq) + H2O(l)
Is the reaction spontaneous? Does it go forward as

written?
If H & S for the reaction are known second law
q
=
in the S
form
can be used to answer the above
T
question.
qp H
The second law for aspontaneous
reaction at
S> =
T T
constant P:
H
S>
T

H
- S 0
T
H - TS 0 (-ve)

(spontaneous reaction, constant T and P)


prediction: reaction is spontaneous left to right as
written
H - TS 0 ( ve)
prediction: reaction is non-spontaneous left to right

as written
reaction is spontaneous in the opposite direction
H - T S =0
reaction is at equilibrium

Gibbs Free 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

Gibbs Free Energy


If T & P are constant, the relationship

between the sign of G and the spontaneity


of a reaction:

(i) If G = -ve, reaction is spontaneous in the


forward reaction
(ii) 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

Standard Free Energy


Change
Standard free energies of formation, Gof ,are

useful in calculating the standard free energy


change for chemical process

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

G0 tells whether a mixture of


reactants and products (under standard
conditions):
(i) would spontaneously react in the forward
direction to produce more products G0 < 0
(ii) or in the reverse direction to form more

Quantity of

Example 11
(a) Calculate the standard free-energy change for the

following reaction at 298 K:


N2(g) + 3H2(g) 2NH3(g)
(b) What is G0 for the reverse of the above reaction?
Solution
(a)G o 2 molG o NH 1molG o N 3 molGo H
f
3
f
2
f
2

kJ
2 mol -16.66

mol

- 33.32kJ

kJ
kJ

1mol 0 mol 3 mol 0 mol

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

Free Energy and


Temperature
Consider equation :

G = H (enthalpy term) - T S (entropy


term)
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 & magnitude of G.
Example: melting of ice liquid water (P = 1 atm)
H2O(s) H2O(l), H > 0, S > 0
endothermic process, H = +ve
Generally

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

At T < 00C, magnitude of

When T > 00C, magnitude of -TS > magnitude of

H
-ve entropy term dominates, leading to a negative
value of G
Melting of ice is spontaneous at T > 00C

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

Example 12
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 5000C

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

T = 500 + 273 = 773 K


J
G 92.38kJ - 773K -198.3
K

- 92.38kJ 153kJ
61kJ
o

1kJ

3
10 kJ

The End