CHM271

CHAPTER 2 :
THERMODYNAMICS
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 CHAPTER 2: THERMODYNAMICS
2.1 Types of System (open, closed, isolated)
2.2 First Law of Thermodynamics
2.2.1 Internal energy, work (pressure-volume) and heat
2.2.2 Reversible and irreversible processes
2.3 Second Law of Thermodynamics
2.3.1 Entropy change and spontaneity of reaction
2.3.2 Gibbs free energy
 INTRODUCTION

THERMODYNAMICS
Study of energy change of chemical / physical processes

 Provide useful guidelines for understanding

the energetic & the direction of the process.
 Assume that the universe can be divided into
a system and its surroundings.
 SYSTEM & SURROUDING

SYSTEM
The specific part of the universe that is of
interest in the study

SURROUNDING
The rest of the universe

BOUNDARY
Can be as real as the walls that separates the
system from surrounding
 TYPE OF SYSTEM
Depends on the direction of matter & energy transfer
OPEN
 Both matter & energy can be transferred
between system and surroundings.
 Water in tumbler placed in open area

CLOSED
• Energy but no matter can be transferred
between system & surroundings.
 Hot water in steel box

ISOLATED
SYSTEM
 Neither matter nor energy can be transferred
between system and surroundings
 Hot coffee in thermos flask
 FIRST LAW OF THERMODYNAMICS

DEFINITION
Energy can be converted from one to another but cannot be created or
destroyed. It may change from one form to another.

 Energy is being transferred between system & surrounding.

Hot coffee get cooled off when exposed to surroundings

Energy lost by coffee = Energy gained by Surroundings
 INTERNAL ENERGY, E
INTERNAL ENERGY
 total energy of a system. (kinetic + potential)
 Sum of all kinetic & potential energies of all component of
the system.
 the energy of a system can be changed as work or heat.
 Units : joules (J) or calorise, 1 cal = 4.184 J
 for molar energy ; J/mol

CHANGE IN INTERNAL ENERGY

• Absolute internal energy cannot measured, only in internal
energy

ΔE = Efinal - Einitial
 INTERNAL ENERGY, E

DEFINITION
when a system undergoes a physical or chemical change, the E is given
by the heat absorb/release by the system plus work done on/by the
system.

ΔE = q + w
ΔE = Internal energy
q = Heat change between system & the surrounding
w = Work done on / by the surrounding
 Process Sign
Exothermic -
Endothermic +
Work done on surrounding -
Work done by surrounding +

** Gas expand, q is positive because heat is added during the expansion.

EXAMPLE
In a certain process, 600 J of work is done on the system
which gives off 250 J of heat.
Determine the change in internal energy for the process Ans : 350J

w = + 600J SOLUTION
SYSTEM
q = - 250J

ΔE = q + w
 WORK, W
DEFINITION
energy transfer between system and surroundings due to force
acting through distance.
 Work is done when an object is moved against some opposing
force.
 eg; Expansion wok= gas expanding
driving force against atmospheric pressure
 The amount of work of expansion done by the reaction:

w = work (J)
w = - P*ΔV
P = Pressure (atm)
ΔV = change in the volume (L)
= Vfinal – Vinitial
*In vacuum, pressure is 0
EXAMPLE w = - PΔV

SOLUTION
 W, FOR IDEAL GAS BEHAVIOR
w = work (J)
 Involve moles
n = Number of moles (mol)
R = Gas Constant (8.314 J/mol K)
T = Temperature (K)
Vi = Initial Volume (L)
EXAMPLE Vf = Final Volume (L)

Calculate the work done when 2 moles of an ideal gas initially at 25

°C at 1 atm expands from 0.025 L to 0.05 L. (R = 8.314 J/mol K)

w
SOLUTION

= - 3 436.37 J
 HEAT, q

DEFINITION
Energy transfer between system and surroundings due to a
temperature difference

q = msΔT @ q = CΔT
q = Heat (J)
s = Specific Heat (J/g K or J/g °C)
C = Heat Capacity (J/K or J/°C)
ΔT = Temperature Changes (K or °C )
= Tfinal - Tinitial
 SPECIFIC HEAT , s

DEFINITION
Amount of energy required to raise the temperature of
1g of a substance by 1K or 1°C

C = ms
C = Heat Capacity (J/K or J/°C)
m = mass (g)
s = Specific Heat (J/g K or J/g °C)
 HEAT CAPACITY, C

DEFINITION
Amount of heat required to raise the temperature of a
substance by 1K or 1°C

 For gases, it is necessary to distinguish the heat capacity which

apply to the condition of constant pressure & volume.

constant pressure, constant volume,

ΔP = 0 ΔV = 0
 HEAT, q

EXAMPLE
Determine the heat absorbed when the temperature of 15.0 g of water is
raised from 20°C to 50°C. Given specific heat of water is 4.184 J/g K

heat absorbed = Positive sign of q SOLUTION

ΔT = (50 - 20)°C = 30°C
@
SYSTEM
= (323.15 – 293.15) K = 30 K
q = +1.88 kJ
q = msΔT
= 15.0g × 4.184 J/g K × (30K)
= 1882.8 J
= + 1.88 kJ
 HEAT, q

EXAMPLE
Determine the heat that is given off when an 869 g iron bar cools from
94°C to 5°C. Given specific heat of Fe is 0.444 J/g K

SOLUTION
Heat given off = Negative sign of q
ΔT = (5 – 94)°C = -89°C = -89 K SYSTEM
q = msΔT q = - 334.3 kJ
= 869g × 0.444 J/g K × (-89K)
= - 34,339.4 J
= - 34.34 kJ
 HEAT, q

ADIABATIC Process that takes place in a system without heat

exchange between the system & surroundings, q = 0
 A system in which heat is not allowed in or out
 The system does work on the surroundings, w is negative.
 There is decrease in the system energy.
 This can be achieved by insulating the system.

q=0
ΔE = q + w
ΔE = 0 - w
ΔE = -w
 HEAT, q
ISOBARIC
Thermodynamic process taking place at constant pressure, ΔP = 0
 When an isobaric reaction is carried out, the heat given off or absorbed
during a chemical reaction at constant pressure is equal to the change
in the enthalpy of the system.
 Thus, heat, qp transferred is equal to the change in the enthalpy, ΔH.

qp = ΔH
@
qp = nCpΔT
5
where Cp = R
2
 HEAT, q
ISOCHORIC
Thermodynamic process taking place at constant volume, ΔV = 0

 When an isochoric reaction is carried out, the heat, qv transferred is

equal to the change in the internal energy, ΔE.
ΔE = q + w
ΔE = q - PΔV qv = nCvΔT
ΔE = q - P(0) @ 3
where Cv = R
2
qv = ΔE
 HEAT, q
ISOTHERMAL
Thermodynamic process taking place at constant temperature, ΔT = 0
 Temperature, T is constant throughout the process.
 To achieve this, one encloses the system in thermally conducting walls
and places it in a large constant temperature bath.
 For a perfect gas, E is a function of T,

ΔE = 0 when ΔT = 0
ΔE = q + w
qT = -w
 REVERSIBLE PROCESS

DEFINITION
A process in which the backwards reaction (products → reactants)
takes place relatively easily under certain conditions.
 Reversible process occur when
 The products can react to produce the original reactants again.
 Can restore both system and surroundings to their initial state.
 IRREVERSIBLE PROCESS

DEFINITION
A process in which the products that are made cannot readily be
changed back into their reactants
 Most chemical reactions are considered irreversible
 They go to completion and cannot be reversed easily.
 System and its surroundings cannot both be restored
to their initial conditions
 All spontaneous processes are irreversible.
 All real processes are irreversible.
THERMAL PROCESS
 SECOND LAW OF THERMODYNAMICS

DEFINITION
The entropy of the universe increases in a spontaneous process and
remains unchanged in an equilibrium process.

Spontaneous process: ΔSuniv = Δ Ssys + Δ Ssurr > 0

Equilibrium process: Δ Suniv = Δ Ssys + Δ Ssurr = 0

Suniv = Entropy of universe (J/K mol)

Ssys = Entropy of system (J/K mol)
Ssurr = Entropy of surrounding (J/K mol)
 SPONTANEITY
SPONTANEOUS PROCESSES
 A reaction which occur under the given set of condition
 processes are those that can proceed without any outside intervention.

NON SPONTANEOUS PROCESSES

 A reaction does not occur under specified conditions.
Spontaneous Non Spontaneous
A ball rolling downhill A ball rolling uphill
Sugar dissolves in water form Dissolved sugar reappear in original
Iron forms rust Rust change back to iron
 LARGE numbers of exothermic reactions are spontaneous.
 Even though exothermicity favors the spontaneity but does not
guarantee it.
 Need another thermodynamic quantity : ENTROPY
 ENTROPY, S

DEFINITION
Measure of the randomness or disorder of a system
 Greater the disorder of a system, the greater its entropy
 More ordered a system, the smaller its entropy.
 For any substance, the solid state is more ordered than
the liquid state and the liquid state is more ordered than
gas state
 S0 must be positive value for the reaction to be
spontaneous/favorable.
Processes that lead to an increase in entropy (ΔS > 0)
 STANDARD ENTROPY, S°

DEFINITION
The absolute entropy of a substance at
standard condition.

 Units : J/K or J/K mol

 Positive value of ΔS° indicates
spontaneous/favorable reaction & vice
versa.
 ENTROPY CHANGES, ΔS°
 In general, entropy increases when
 Gases are formed from liquids and solids.
 Liquids or solutions are formed from solids.
 The number of gas molecules increases.
 The number of moles increases.
 If a reaction produces more gas molecules than it consumes, ΔS° > 0.
 If the total number of gas molecules diminishes, ΔS° < 0.
EXAMPLE Predict the processes that will lead to an
increase in the entropy of the system.
Tips : Compare the state of matter & number of molecules
SOLUTION ΔS
a) N2(g) + 3H2 (g) ⇋ 2 NH3(g)
Total number of gas molecules decreases in this reaction.
Thus, the system becomes more ordered.

b) H2O(l) ⇋ H2O(g)
Gases (product) are more disordered than the corresponding liquids
(reactant)
c) CaCO3(s) → CaO(s) + CO2(g)
Decomposition from solid (reactant) gives two products (solid & gas).
Formation of gas molecule leads to an increase in entropy because the
system becomes more disordered.

d) NH4NO3(s) + H2O(l) → NH4+ (aq) + NO3- (aq)

The NH4+ and NO3- ions (products) are free to move in a random fashion
through the aqueous solution, whereas these ions are locked into position
in the crystal. As a result, the randomness increases.
 SPONTANEITY

STANDARD ENTROPY OF REACTION , ΔS°sys

The entropy change for a reaction carried out at 1 atm and 25°C.

aA + bB → cC + dD

ΔS°sys = ∑nS° (Products) - ∑nS° (Reactants)

ΔS°sys = [cS°(C) + dS°(D)] - [aS°(A) + bS°(B)]

 S° for each component is found in a table.
 SPONTANEITY

EXAMPLE Calculate the standard entropy change for the

following reaction at 25°C.

2CO (g) + O2 (g) → 2CO2 (g)

S°(CO) = 197.9 J/K mol S°(CO2) = 213.6 J/K mol

S°(O2) = 205.0 J/K mol

SOLUTION
∆S°sys = [2 x S° (CO2)] – [2 x S° (CO) + S0 (O2)]
= [2 x 213.6 J/K mol] – [(2 x 197.9 J/K mol) + 205 J/K mol]
= 427.2 – [395.8 + 205.0] J/K mol
= -173.6 J/K mol
 SPONTANEITY

STANDARD ENTROPY OF SURROUNDING , ΔS°surr

Expression of entropy in terms of the enthalpy change for the system, ΔH

ΔH = Enthalpy change of system (J or J/mol)

T = Temperature (K)
 EXAMPLE
Determine ΔSsurr and ΔSuniv for the vaporization of 1.00 mole of
water at 125°C. Given ΔHsys = 40.7 kJ/mol and ΔSsys= 119 J/K
for 1 mole of water vaporizing.)

SOLUTION

= ΔS
surr ΔS sys
ΔS +
univ
ΔS = - 102.22 J/K mol + 119 J/K.mol
univ
ΔS = +16.78 J/K mol
univ
 GIBBS FREE ENERGY, G

DEFINITION
The energy available to do useful work
 Some reactions are spontaneous because they give off energy in the
form of heat (∆H < 0, Exothermic).
 Others are spontaneous because they lead to an increase in the
disorder of the system (∆ S > 0).
 What happens when one of the potential driving forces behind a
chemical reaction is favorable and the other is not?
 Quantity known as the Gibbs free energy (G) of the system, which
reflects the balance between these forces.
 Negative value of ΔG° indicates spontaneous/favorable reaction &
vice versa.
ΔG < 0
spontaneous
 GIBBS FREE ENERGY
ΔG = ΔHsys –T ΔSsys @ ΔG°= ΔG°f (product) - ΔG°f (reactant)
G = Gibbs Free Energy (J or J/mol)  Standard free energy of formation (ΔG°f ) is
the free-energy change for the formation of
ΔHsys = Enthalpy change (J or J/mol) 1 mole of the substance from its elements
= ΔH°f (product) - ΔH°f (reactant in their standard states,
T = Temperature (K)  Substances with negative values for ΔG°f
are stable & do not decompose into their
ΔSsys = Entropy Change (J/K moll)
constituent elements.
 enthalpy of the system minus the change  Use a table of G°f values for reactants and
in the product of the temperature times products to calculate ΔG°.
the entropy of the system.  G°f = 0 for elements in their standard states
(their naturally occurring form at 25°C)
 If the data are collected under standard
state conditions, the result is the Favorable/ Unfavorable /
standard - state free energy of reaction spontaneous Non spontaneous
(Go). ΔG° - +
 ΔG = 0, the reaction/process is at ΔH° - +
equilibrium ΔS° + -
 EXAMPLE
The following reaction occurs at 25o C.

N2(g) + 3H2(g) → 2 NH3(g)

Determine the spontaneity of reaction from the value of Go for this reaction
by using the given information:

Compound ΔH° (kJ/mol) ΔS° (J/K mol)

N2(g) 0 191.61
H2(g) 0 130.68
NH3(g) - 46. 192.45
 SOLUTION
∆Hosys
ΔG = ΔHsys –T ΔSsys
= ∆ Hfo (products) - ∆ Hfo (reactants)
= [2 x -46.11 kJ/mol] - [0 kJ/mol]
Spontaneity?
= - 92,220 J/mol
∆Sosys
= ∆So(products) - ∆So(reactants)
= (2 x 192.45 J/K mol) – [(1 x 191.61 J/K mol) + (3 x 130.68 J/K mol)]
= - 198.75 J/K mol
∆Gosys
= ΔHsys –TΔSsys
= - 92,220 J/mol - (298.15 K x -198.75 J/K mol)
= - 92,220 + 59257.31 J/mol At 25o C, ∆Gosys is negative,
= - 33 kJ Thus, the reaction is
spontaneous at 25o C.
 PRACTICE
Calculate the standard free energy change for the formation of NO(g)
from N2(g) and O2(g) at 298 K:
N2(g) + O2(g) → 2 NO(g)

Given that ΔH° = 180.7 kJ and ΔS° = 24.7 J/K. Determine the
spontaneity of the reaction under these circumstances?

‘
 PRACTICE
Question 1
A sample of nitrogen gas expands in volume from 1.6 L to 5.4 L at constant
temperature. Determine the work done in joules if the gas expands :
(a)against a vacuum
(b)against a constant pressure of 4 atm?

Question 2
Identify whether the following process is spontaneous or not.

a)Ice cube melts

b)2NO(g) + O2(g) → 2NO2(g)
Question 3
PRACTICE
Given the following entropy values :
Al2O3(s) = 51.00 J/K mol; Al(s) = 28.32 J/K mol
H2O(g) = 188.7 J/K mol; H2(g) = 130.6 J/K mol
a)Determine ∆S for the reaction:
Al2O3 (s) + 3H2 (g) → 2AI (s) + 3H2O (g)
b)Give a conclusion from the result in term of the randomness.

Question 4
Combustion of ethanol at 298 K is given by the reaction below:
C2H5OH(g) + 3O2(g) → 2CO2(g) + 3H2O(l)
The followings are standard molar entropy of sustances at 298 K.
C2H5OH(g) = 386.1 J/K mol ; O2(g) = 205 J/K mol;
CO2(g) = 213.7 J/K mol ; H2O(g) = 69.9 J/K mol
Determine the entropy changes, for the combustion of ethanol at 298 K
using the data above. State the procss is spontaneous or non spontaneous.
Question 5 PRACTICE
CaCl2 dissolves in water as follows:
CaCl2(s) → Ca2+ (aq) + 2Cl– (aq)

a)Determine ΔG° for this process at 25°C using the following G°f values :
CaCl2(s) = −748.1 kJ/mol; Ca2+ (aq) = − 553.6 kJ/mol;
Cl–(aq) = − 131.2 kJ/mol.
a)Predict the spontaneity of reaction.

Question 6
Determine the free energy change (ΔG°) for the following reactions using
the standard free energy of formation values given below, then indicate if
the reaction is spontaneous.
ΔG°f (NO)=+90.3 kJ/mol and ΔG°f (NO2)=+33.2 kJ/mol

a)N2(g) + O2(g) → 2 NO(g)

b)2 NO(g) + O2(g) → 2 NO2(g)
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