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 of thermodynamics
3. Calculate the change in internal energy
2
 Thermochemistry
Chapter Outline
 Forms of Energy and Their Interconversion
 Enthalpy: Heats of Reaction and Chemical
Change
 Calorimetry: Laboratory Measurement of Heats
of Reaction
 Stoichiometry of Thermochemical Equations
 Hess’s Law of Heat Summation
 Standard Heats of Reaction
 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 thermodynamics,
deals with heat involved in chemical reaction.
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 motion
Forms of Energy and Their Interconversion

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

7
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 system’s 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

 Total change in a system’s 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
 Heat out from a system – hot water in a beaker
System: hot water
q = -ve as heat was lost by the system.
E = -ve

 Heat into a system - Ice water in a beaker

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 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
 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

 q = +ve : system gains heat, q = -ve: system loses

energy
 w = +ve: work done on system, w = -ve: work done by
system
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
 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
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)
kgm
 where F = mass (m) x acceleration (a) in units of 2
s
 w =
kgm kgm2
2
xm 2
J
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 car’s 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,
E =q+w
= -325 J + (-451J) = -776 J
 State Functions and the Path Independence of
the Energy Change
 System’s 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
 For a given change, E (sum of q and w) is constant, even
though the specific values of q and w can vary
 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
Enthalphy: Heats of Reaction and Chemical
Change
The Meaning of Enthalphy
 Heat & work must be measured to determine E
 Two most important type of chemical work
(i) electric work - work done by moving charged
particles
(ii) PV work - work done by expanding gas

 PV work
Quantity PV work = multiple the external pressure (P) by
the change in volume of the gas (V, or Vfinal - Vinitial)

w = -PV
 e.g. In an open flask, a gas done work by pushing back
the atmosphere.  work done on the surroundings is -ve
because the system loses energy

w = -PV (2)

 For reactions that occur at constant pressure, a

thermodynamics variable called enthalphy (H) eliminates
the need to consider PV work.

 Enthalphy, a thermodynamic prop. of a system is defined

by H = E + PV,
Change in enthalphy, H = E + PV
 Combining Equations (1) and (2)
E = q + w = q + (- PV) = q - PV (3)

 At constant pressure, q = qp
E = qp - PV
qp = E + PV (4)
where E + PV = H
 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, PV  0, H  E
(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, PV = 0, H  E

(iii) Reactions in which the amount (mol) of gas does

change. PV  0, qp is usually much larger than PV
 From equation (4), qp = E + PV = H,

 E = qp - PV = H, E  qp  H,  E  H

 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

 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
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 of compound is

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

(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
 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
 q  T or q = constant x T or q/T = constant
 Heat capacity, C = q/T = quantity of heat required to
change the temperature of substance by 1K. (Unit: J/K)
 Specific heat capacity, c = q/m T = quantity of heat
required to change the temperature of 1 gram of a
substance by 1K (Unit: J/g.K)
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 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 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 (1.5)

 -(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 100.00 0C
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.
 Calculating csolid
J
4.184 x 50.00 g x 3.93K
cH O x massH O x ΔTH O gK
c solid   2 2 2

masssolid x ΔTsolid 25.64 g x (71.51K)
J
 0.387
gK
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 manufacturer’s claim
correct? (Heat capacity of the calorimeter =
8.151 J/K)
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
Formation of 2 mol water (exothermic):
2H2(g) + O2(g)  2H2O(l) 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 Hrxn = -576 kJ
Hess’s Law of Heat Summation

 Hess’s 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 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 sides of
equations). Add their H values to obtain the
unknown H
Example
 Application of Hess’s Law:
Oxidation of 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) H1 = -296.8 kJ

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)
= -396.0 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.
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) H0f = -74.9 kJ
 Example
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 = -127.0 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
 Determining H0rxn from H0f values of
Reactants and Products

 By applying Hess’s Law, H0f values can be used to

determine H0rxn for any reaction:

H0rxn = mH0f (products) - mH0f (reactants)

Suppose we want H0rxn for:

TiCl4(l) + 2H2O(g)  TiO2(s) + 4HCl(g)

H0rxn = {H0f [TiO2(s)] + 4H0f [HCl(g)]} - {H0f [TiCl4(l) + 2H0f 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 = mH0f (products) - mH0f (reactants)
= {4H0f [NO(g)] + 6H0f [H2O(g)]} - {4H0f [NH3(g)] +
5H0f [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 = -906 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
 sign of H - not enough to predict whether the reaction
will proceed
 H - not the only factor governs reactants or
products favoured
 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

 Temperature: have an impact on the spontaneity

 e.g. endothermic process of melting ice, at T  0 C:
0
ice melts spontaneously
reverse process (liquid water  ice), nonspontaneous
0
 But at T 0 C:

liquid water converts into ice spontaneously

conversion of ice liquid water, not 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
(ii) 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
 S = Sfinal – Sinitial

 S of a system  to the disorder of the system

 Ssystem  0, implies the system becomes more disordered

 Ssystem  0, implies the system becomes less disordered

 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
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
 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
 In general - entropy increasing with increasing temp.
 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
Calculation of Entropy Change
 Standard molar entropies, S0 - molar entropy values
of substances in their standard states
 Entropy change in a chemical reaction, S0:

Δ So =Σ nSo (products ) - Σ n So (reactants )

 = “sum of”
n = amounts (mol) of the products
m= 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 
ΔS  2 mol 1925   1 mol 191.5   3 mol 130.6 
 mol K    mol K   mol K 
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
 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

 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
 The change in entropy, S, of the system at a given
temperature:
q
ΔS  entropy created 
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
 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 absolute
temperature, q
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
ΔS  equilibrium process, (Eq.1)
T
 Examples of phase changes under equilibrium:
 vaporization of a liquid, fusion of a solid
 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 = heat of fusion, Hfus

q
ΔS =
T
 entropy change , Δ Hf us
Δ S=
T

where T = absolute temp. of the phase transition, 373K

Note: S - usually express in joules per Kelvin
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?
 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 left to right as

written?
 If H & S for the reaction are knew  second law in the
form ΔS = q can be used to answer the above question.
T
The second law for a spontaneous reaction at constant P:
qp Δ H
Δ S> =
T T
ΔH
Δ S>
T
 ΔH
- ΔS  0
T

ΔH - TΔS  0 (-ve)

(spontaneous reaction, constant T and P)

 prediction: reaction is spontaneous left to right as written

ΔH - TΔS  0 (ve)

 prediction: reaction is non-spontaneous left to right as written

Δ H - TΔ S = 0
reaction is spontaneous in the opposite direction
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 - TS
 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

ΔGfo  Σn ΔGfo (products)  Σm ΔGfo (reactants )

 = “sum of”
n = amounts (mol) of products
m = amounts (mol) of reactants
 Quantity of 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 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 G0 for the reverse of the above reaction?

Solution
o
 o
 
(a)ΔG  2 mol ΔGf NH3   1 mol ΔGf N2   3 mol ΔGf H2 
o o

  kJ    kJ   kJ 
 2 mol   - 16.66   1 mol   0   3 mol   0 
  mol    mol   mol 
 - 33.32 kJ

(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)

 Generally H & S change very little with T. However, the

value of T directly affects the magnitude of -TS
 As T increases, the magnitude of the term -TS 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
 entropy increases during process, S = +ve, -TS = -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 -TS > 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 & -TS are equal in magnitude.  G = 0
 Under standard conditions (at 250C)
G0 = H0 - TS0
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 5000C
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 G

under non-standard conditions
(ii) How to directly relate the G0 for a reaction to the
value of the equilibrium constant for the reaction
 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
 Note: Suppose the general equilibrium equation:
aA + bB  pP + qQ
a, b, p & q = coefficients in balanced chemical equation

equilibriu m constant , K 
P Q
p q

A a Bb
 Q is calculated by substituting reactant and product
concentrations in the equilibrium-constant 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 = G0 + RT ln K
G0 = -RT ln K

  ΔGo 
K  exp  
 RT 
The End