CHM 271

CHAPTER 1
THERMODYNAMIC
Mardhiah Ismail
 Outline
• 1.1Types of system
• 1.2 First law of thermodynamic
o 1.2.1 internal energy
o 1.2.2 Specific heat and heat capacity
o 1.2.3 Concept of enthalpy
o 1.2.4 Effect of temperature on enthalpy
o 1.2.5 Reversible and non reversible process
o 1.2.6 Types of thermal process

• 1.3 Second Law of Thermodynamic

o 1.3.1 Entropy change and spontaneity
o 1.3.2 Gibbs free energy
o 1.3.3 Dependence variable of entropy
• Define the 1st and 2nd law of thermodynamics

• Calculate work (W), heat (q) and change in internal

energy (∆E)

•Calculate ∆H, ∆S⁰ and ∆G⁰

•Identify the spontaneity of a reaction

 1.1 Types of System
• Definition :
o System : specific part of the universe being investigate.
o Surrounding : the rest of the universe outside the system
o Universe : system + surrounding

• System can
o Absorb/release heat
o can do work / can have work done for it

• Types :
o Open system : can exchange energy and mass
o Closed system : can exchange energy not mass
o Isolated system : can not exchange energy and mass
Three types of systems
 Thermodynamic
• What is Thermodynamics?
o Study of the energy changes that accompany physical
and chemical changes

• What does Thermodynamics tells us?

o Energy changes associated in the reaction
o Equilibrium position of reacting system
o Spontaneity of a reaction
o Maximum efficiency of a heat engine
o etc
 The Law of
Thermodynamic
• Thermodynamic is the study of interconversion of
heat, energy and work

o First Law: Energy is conserved; it can be neither created nor

destroyed. It can only change form.

o Second Law : In an isolated system, natural processes are

spontaneous when they lead to an increase in disorder, or
entropy.

o Third Law : The entropy of a perfect crystal is zero when the

temperature of the crystal is equal to absolute zero (0 K).
 1.2 The First Law
• 1stlaw of thermodynamic states that the energy of
the universe is constant.

• Energy can be transferred from the system to its

surroundings, or vice versa, but it can't be created
or destroyed.

ΔE system + ΔE surroundings= ΔE universe= 0

 1.2.1 The First Law
Internal Energy
• Internal energy (E) is the sum of the kinetic and potential
energies of the particles that form the system.

• •The internal energy of the system is still proportional to

its temperature.

• Any change in the internal energy of the system is equal

to the difference between its initial and final values.

ΔE= Ef –Ei
 The First Law
Internal Energy
• The change in the internal energy of a system is
equal to :
o the sum of the heat gained or lost by the system
o the work done by or on the system.

ΔE= q+ w
 The First Law
Internal Energy
• The internal energy and temperature of a system
decrease (E< 0) when the system either loses heat
or does work on its surroundings.

• •The internal energy and temperature increase (E>

0) when the system gains heat from its surroundings
or when the surroundings do work on the system.
 The First Law
Internal Energy
• Numerical value of q and w can be either positive
or negative
 Example 1.1
The work done when a gas is compressed in a cylinder is 462 J. During
this process, there is a heat transfer of 128 J from the gas to the
surroundings. Calculate the energy change for this process.

Answer:
Compression is work done on the gas, so the sign for w is positive, w =
462 J, whereas q is negative because heat is transferred from the
system to the surrounding, q = -128 J.

∆E = q + w
= -128 J + 462 J
= 334 J
 Example 1.2
When petrol burns in an engine, CO2 and H2O are formed and cause
the volume to expand by pushing the piston upward. The work done by
the system (pushing the piston) is 415 J and the system lost 350 J of
heat to surrounding, calculate the change in energy. DE in kJ

Work is done by the system, so w= -415 J

Heat is released by the system, so q = -350 J

DE sys= q + w
DE = -350 + (-415) = -765 J
= -0.765 kJ
 1.2.2 Specific Heat and Heat Capacity
Specific heat (s) : amount of heat required to raise its temperature of 1g of
substance by 1oC

Heat capacity (C) : amount of heat required to raise its temperature of a

given quantity of substance by 1oC

Heat capacity = mass x specific heat

C = m.s

Heat (q) absorbed or released:

q = m.s. Dt
q = C. Dt
Dt = tfinal - tinitial

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How much heat is given off when an 869 g iron bar cools
from 94oC to 5oC?

s of Fe = 0.444 J/goC

Dt = tfinal – tinitial = 5oC – 94oC = -89oC

q = msDt = 869 g x 0.444 J/g oC x –89oC

= -34,000 J

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 1.2.3 Enthalpy, H

• The change in the enthalpy of the system during a chemical

reaction is equal to the change in the internal energy plus the
change in the product of the pressure of the gas in the system
and its volume.
∆H = ∆E + ∆PV
• When gases are involved in reactions, the volume changes
may be significant and need to be considered
(assume that the gases in the reaction behave as ideal gases)

∆H = ∆E + ∆nRT
• ∆ n= moles of gas(product) –moles of gas(reactant)
• The heat supplied at constant pressure is equal
to the change in enthalpy, H.

H = E + PV

• The change in enthalpy at constant pressure;

DH = DE + PDV

• When gases are involved in the reaction;

PDV  DnRT : ideal gas law

*Dn = mole of gas product – mole of gas reactant

DH = DE + DnRT
 A Comparison of DH and DE

2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) DH = -367.5 kJ/mol

DE = DH - PDV At 25 oC, 1 mole H2 = 24.5 L at 1 atm
PDV = 1 atm x 24.5 L = 2.5 kJ

DE = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol

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 The difference between DE and DH is usually small, so 2
values are almost equal and in many cases DE = DH

 Consider the following case:

a) Reaction which Dn = 0, mol of gases between

reactant and product are equal
b) Reaction with no gas involved, negligible change in
volume, DV ~0
c) Reaction when mol of gas change, PDV is not zero,
qp >>> PDV, so DE ~ DH

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• The relationship between the change in the internal
energy of the system during a chemical reaction
and the enthalpy of reaction can be summarized
as follows:

o The heat given off or absorbed when a reaction is run at constant

volumeis equal to the change in the internal energy of the
system.
∆Esys=qv

o The heat given off or absorbed when a reaction is run at constant

pressure is equal to the change in the enthalpy of the system.
∆Hsys=qp
 Effect of temperature on Enthalpy
• Enthalpy changed when temperature changed.
• Enthalpy change is the measurement of heat at
constant pressure, qp.

Heat capacity, C = q/∆T

Specific heat = q/mass (∆T)
q = specific heat x mass x ∆T
∆H=q/n
Example 1.3: Calculate the change in internal energy
when 2 moles of CO are converted to 2 moles of CO2 at
250C

2CO (g) + O2 (g)⟶ 2CO2 (g) DH =-566.0 kJ

Dn = 2mol-3 mol
= -1 mol

From equation, we write;

DE = DH - DnRT
= -566.0 kJ-(-1mol)(8.314J/K.mol)(298)
= -563.5 kJ

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 Example 1.4: The heat of combustion of methane, CH4 at
constant volume is -885.2 kJ/mol. What is the enthalpy of
the reaction at 250C?

CH4 (g) + 2O2 (g) ⟶ CO2 (g) + 2H2O (l) DH =-885.2 kJ

Since the reaction is at constant volume, DE = qv = -885.2 kJ

Dn = 1mol-3 mol
= -2 mol

DH = DE + DnRT
= -885.2 x 10-3 J + (-2 mol)(8.314J/K.mol)(298K)
= -890155 J = -890.2 kJ

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1.2.5 Reversible and Irreversible Processes

•There are 2 main type of thermodynamic processes;

reversible process
irreversible process.

•In a reversible process the system changes in such a

way that the system and surroundings can be put back in
their original states by exactly reversing the process.

•Also known as an equilibrium process.

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• Irreversible processes cannot be undone by exactly reversing the
change to the system.

• Process which both the system and surroundings cannot return to their
original conditions.

• System is not at equilibrium.

• Spontaneous processes are irreversible.

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 Reversible Process
• In a reversible process the system changes in such a
way that the system and surroundings can be put
back in their original states by exactly reversing the
process.

• Changes are infinitesimally small in a reversible

process.
 Irreversible Process

• Irreversible processes cannot be undone by exactly

reversing the change to the system.
o All Spontaneous processes are irreversible.
o All Real processes are irreversible
Irreversible Process
Reversible and irreversible
 1.2.6 Types of Thermal Process
4 basic processes:
• Isobaric, P = const
• Isometric, V = const
• Isothermal, T = const
• Adiabatic, Q = 0
 Isothermal Process
A process in which the temperature of the system
remains constant.

Isothermal expansion is an increase in volume, but

temperature constant so pressure ↓

For an ideal gas, this process implies that volume and pressure of
product are constant

P1V1 = P2V2= constant

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 Work and heat exchange
in the reversible isothermal
compression process

During the expansion, work is done by the

system on the surroundings of magnitude

Integrate:

At the end of isothermal expansion,

1.The surroundings have received
work, W
2. The surroundings have given up
heat, q is equal to W
Work and heat transfer in
reversible isothermal expansion

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Calculation of internal energy, ∆E

During isothermal expansion process, temperature

constant, so ∆E = 0 (internal energy E of an ideal gas
depends only on temperature)
Calculation of enthalpy, ∆H

H = E + PV
So, ∆H= ∆ (E + PV)
= ∆E + ∆PV
= ∆E + ∆nRT
Calculation of q and w

From first law of thermodynamics, ∆E = q + w

As for isothermal process, ∆E = 0
So, w =- q
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Example 1.5:
Calculate q, w, ∆U and ∆H for the reversible isothermal expansion
of one mole of an ideal gas at 37oC from a volume of 20dm3 to a
volume of 30 dm3

Solution:
Since isothermal process ⟶ ∆E and ∆H are zero
Work can be calculated using

W = nRT ln (V2/ V1)

= (1 mol) (8.314 J K-1 mol-1) (310 K) ln (30 dm3 / 20dm3)
= 1045.02 J

From first law, ∆U= q + w

Since ∆U=0, q = – w = -1045.02 J

∆U = ∆E 37
 Adiabatic Process
There is no transfer of heat to or from the system, so
q = 0, but ∆T ≠ 0

From first law of thermodynamics, ∆E = q + w

As for adiabatic process, q = 0
So, ∆E =w
W= P ∆V
So ∆E =P ∆V

Specific heat capacity is related to ∆E given by the equation

nCv = ∆E / ∆T

So, ∆E = nCv ∆T = P ∆V

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 Pressure-Volume Work
• Reactions also do work on their surroundings when the
volume of the system expands during the course of the
reaction.

• Heat is required in the process (expansion) for the gas to

perform the external work

W = -P∆V , unit: (N/m2) m3= N.m or L.atm

• PV work: change in pressure and volume

• P constant ⟶V change

• V constant ⟶ P change
 Pressure-Volume Work

Isobaric-Constant pressure, Cp
Most chemical reaction are conducted at
constant pressure

Consider a system which the pressure is

held constant

The work done by the system in

expansion from Va to Vb is given by
w = -P (Vb-Va) = -P∆V

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 Isobaric-Constant pressure, Cp
When gas is heated at constant P it will caused expansion
of gas, ↑V take place,

heat needed (expansion)

w = -PDV

P is the pressure (N/m2 or atm)

DV is the volume (m3 or L) , DV = Vb - Va

W= -P (Vb-Va)
**units for W= N.m or L.atm
Most chemical reaction are conducted at constant
pressure rather constant volume

So the reaction in energy of a system

∆E = qp-P∆V

rearrange

qp = ∆E + P∆V

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 Isometric/Constant Volume,Cv
No external work done when gas is heated at constant
V⟶no PV work is done because no expansion on
system⟶W=0

∆E sys = q + w = q + 0 = qv

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Example 1.6: A sample of nitrogen gas expands in volume from
1.6 L to 5.4 L at constant temperature. What is the work done in
joules if the gas expands (a) against a vacuum and (b) against
a constant pressure of 3.7 atm? ( 1 L.atm = 101.3 Joule)
w = -P DV
w = -P (Vb – Va)
(a) DV = 5.4 L – 1.6 L = 3.8 L P = 0 atm
W = -0 atm x 3.8 L = 0 L•atm = 0 joules

(b) DV = 5.4 L – 1.6 L = 3.8 L P = 3.7 atm

w = -3.7 atm x 3.8 L = -14.1 L•atm

101.3 J = -1430 J
w = -14.1 L•atm x
1L•atm
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Example 1.7: Calculate the work done (in kJoule) during a gas
reaction in which the volume expands from 10.0 L to 13.5 L
against the external pressure of 3.5 atm. Predict the direction of
the heat flow. ( 1 L.atm = 101.3 Joule)

W= -P (Vb – Va)
= - 3.5 atm ( 13.5 L – 10.0 L)
= -12.25 L.atm

-12.25 L. atm x 101.3 J = -1237 J

1 L.atm
= -1.24 kJ

:- the heats flows from the systems to the surroundings.

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Example 1.7
Example 1.8
 1.3 The Second Law (spontaneity)
• 2nd law of
thermodynamic states
that the entropy of the
universe increases in a
spontaneous process and
remains unchanged in
equilibrium process.
• Spontaneous processes are
those that can proceed
without any outside
intervention
• The gas in vessel B will
spontaneously effuse into
vessel A
 The Second Law (spontaneity)
• Processes that are
spontaneous in one
direction are non-
spontaneous in the
reverse direction.
 The Second Law(spontaneity)

• Processes that are spontaneous at one temperature may

be nonspontaneous at other temperatures.
• •Above 00C it is spontaneous for ice to melt.
• •Below 00C the reverse process is spontaneous.
• .
 The Second Law(spontaneity)
• A waterfall runs downhill

• A lump of sugar dissolves in a cup of coffee

• Heat flows from a hotter object to a colder object

• Iron exposed to oxygen and water forms rust

Spontaneous

Nonspontaneous
The Second Law(spontaneity)
 The Second Law (spontaneity)
• Spontaneous process
o favoured by decrease in enthalpy (∆H<0)
o favoured by increase in entropy (∆S>0)

• In chemical reactions, spontaneous reaction can be

either exothermic (∆H<0) OR endothermic (∆H>0).
 Entropy
• Entropy (S) is a measure of the randomness or
disorder of a system.
• Order S disorder S
ΔS= Sfinal-Sinitial

• For any substance, the solid state is more ordered than

the liquid state and the liquid state is more ordered than
gas state
Ssolid< Sliquid<< Sgas
H2O (s) H2O (l) ΔS> 0.
 Entropy
• A change in order is a change in the number of ways of
arranging the particles, and it is a key factor in
determining the direction of a spontaneous process.
 1.3.1 Changes in Entropy
• Process that increase
the entropy of the
system, ΔS> 0
 Changes in Entropy
• In general, entropy
increases when
o Gases are formed from
liquids and solids.

o Liquids or solutions are

formed from solids.

o The number of gas

molecules increases.

o The number of moles

increases.
 Changes in Entropy
• Condensing water vapor
o Randomness decreases

• Forming sucrose crystals from a supersaturated solution

o Randomness decreases

• Heating hydrogen gas from 600C to 800C

o Randomness increases

• Subliming dry ice

o Randomness increases
 Changes in Entropy
• The entropy tends to increase with increases in
o Temperature.
o Volume (gases).
o The number of independently moving molecules.
 Changes in Entropy
• Predict the entropy change for the following
reactions:

1. 2 NH4NO3(s) → 2 N2(g) + 4 H2O(g) + O2(g)

2. 2 SO2(g) + O2(g) → 2 SO3(g)

3. NaCl(aq) → NaCl(s)
 Entropy Changes in the Universe
• The entropy of universe is composed of the system and
the surroundings.
• Therefore,

• DSuniverse = DSsystem + DSsurroundings

• Spontaneous process : DSuniv > 0

• Equilibrium process : DSuniv = 0

Entropy Changes in the Surroundings

Exothermic Process Endothermic Process

DSsurr > 0 DSsurr < 0
 Entropy Changes in the System
The standard entropy of reaction (DS0 ) is the entropy
change for a reaction carried out at 1 atm and 250C.
aA + bB cC + dD

DS0rxn = S nS0(products) - S mS0(reactants)

DS0rxn = [ cS0(C) + dS0(D) ] - [ aS0(A) + bS0(B) ]

S° for each component is found in a table.

Note for pure elements:

 Standard Entropies Value
 These are molar
entropy values of
substances in their
standard states.

 Standard entropies
tend to increase with
increasing molar mass.
 Entropy Changes in the System

What is the standard entropy change for the following

reaction at 250C? 2CO (g) + O2 (g) 2CO2 (g)

S0(CO) = 197.9 J/K•mol S0(CO2) = 213.6 J/K•mol

S0(O2) = 205.0 J/K•mol

DS0rxn = 2 x S0(CO2) – [2 x S0(CO) + S0 (O2)]

DS0rxn = 427.2 – [395.8 + 205.0] = -173.6 J/K•mol

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 Entropy Changes in the System
When gases are produced (or consumed)
• If a reaction produces more gas molecules than it
consumes, DS0 > 0.
• If the total number of gas molecules diminishes, DS0 < 0.
• If there is no net change in the total number of gas
molecules, then DS0 may be positive or negative BUT DS0
will be a small number.
What is the sign of the entropy change for the following
reaction? 2Zn (s) + O2 (g) 2ZnO (s)

The total number of gas molecules goes down, DS is negative.

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 Gibbs Free Energy

For a constant temperature and constant pressure process:

DG = DHsys -TDSsys

DG < 0 The reaction is spontaneous in the forward direction.

DG > 0 The reaction is non-spontaneous as written. The

reaction is spontaneous in the reverse direction.
DG = 0 The reaction is at equilibrium.

This equation shows how DG changes with

temperature. Temperature must be in Kelvin, K

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 Gibbs Free Energy
The standard free-energy of reaction (DG0 ) is the
rxn free-

energy change for a reaction when it occurs under standard-

state conditions.
aA + bB cC + dD
DG0rxn = S nDG0 (products) - S mDG0 (reactants)
f f
DG0 = [cDG0 (C) + dDG0 (D) ] - [aDG0 (A) + bDG0 (B) ]
rxn f f f f

Standard free energy of formation (DG0f ) is the free-

energy change that occurs when 1 mole of the compound is
formed from its elements in their standard states.

DGf0 of any element in its stable form is zero.

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Gibbs Free Energy and Temperature

DG = DH - TDS

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 Effect of temperature on spontaneity

ΔH ΔS ΔG=ΔH – TΔS Spontaneity

-ve +ve -ve Spontaneity at all temperatures
+ve -ve +ve Nonspontaneous at all
temperatures
-ve -ve -ve or +ve Spontaneous at low temperature,
nonspontaneous at high
temperature
+ve +ve -ve or +ve Spontaneous at high
temperature, nonspontaneous at
low temperature

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 Example 1.9:
Given ΔH and ΔS for decomposition of potassium chlorate are
-144 kJ and -36.8 J/K respectively. Calculate ΔG for the
reaction at 250C. Is the reaction spontaneous?
4KClO3  3KClO4 + KCl

Solution:

ΔG= ΔH – TΔS
= - 144 000 J – [(298K)(-36.8 J/K)]
=-133034 J
=-133kJ

The reaction is spontaneous because ΔG is negative

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 Example 1.20:
Hydrogen reduces iron (III) oxide to iron metal.
Fe2O3 + 3H2  Fe + 3H2O
Enthalpy change for the reaction is 98.8 kJ and the entropy change is 141.5 J/K.
a) Is the reaction spontaneous at 40OC
b) What is the temperature for the reaction to be spontaneous?

Solution:

a) ΔG= ΔH – TΔS
= - 98.8 x103 J – [(298K)(141.5 J/K)]
= 56.6 x103 J
= 56.6 kJ

The reaction is nonspontaneous because ΔG is positive.

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b) Since ΔH and ΔS are positive, the reaction will be
spontaneous at high temperature. This temperature can be
estimated by ΔG= ΔH – TΔS = 0, so that ΔG becomes negative,
and the reaction will be spontaneous.

T = ΔH
ΔS
= 98.8 kJ
0.1415 kJ/ K
=698 K
=425OC

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 Temperature and Spontaneity
CaCO3 (s) CaO (s) + CO2 (g)
Equilibrium Pressure of CO2
DH0 = 177.8 kJ/mol
DS0 = 160.5 J/K·mol

DG0 = DH0 – TDS0

At 25 oC
DG0 = 177.8 x 103 – 298(160.5) = 130.0 kJ/mol
Reaction is spontaneous in the reverse reaction

at 835 oC
DG0 = 177.8 x 103 – 1108 (160.5) = 0 kJ/mol
Forward reaction is spontaneous when T > 835 oC

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