Chapter 1: Thermodynamics

Learning Outcomes:

After completing this lesson, student will be able to:

a) Define heat, work and energy

b) Distinguish between exothermic and endothermic reactions

c) Distinguish between open, close and isolated systems

1.1 Basic Concepts

Thermodynamics are the study of the transformations of energy.

The universe is divided into:

1. thesystem is the part which we have a special interest (particular part of the
universe under study)

- Example: reaction of gas in the vessel, an engine, an electrochemical cell, a

biological cell

2. itssurroundings anything else in the universe besides the system where we make
ourmeasurements.

- Example: vessel, the room, the building and so on

The system boundaryseparates the system from the surroundings.

The type of system depends on the characteristics of the boundary that divides it from
the surroundings:

a) Open System

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 The matter and energy can be
transferred through the
boundary between the system
and its surroundings
b) Closed System

- can exchange energy

with its surroundings,
but it cannot exchange
matter

c) Isolated System

- can exchange neither

energy nor matter with
its surroundings

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Work, heat and energy

Thermodynamics is concerned with energy changes that accompanyaprocess.

A process that does work is one that could be used to bring about achange.

- Work is done when an object is moved against an opposing force

- Example: change in the height of aweight somewhere in the surroundings

Energyof a system is its capacity to do work.

- Example :

~ When work is done on a system by compressing a gas or winding aspring,

its capacity to do work is increase and thus the energy of the system is
increased.

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 ~ When the system does work (when piston moves out or the spring unwinds),
its energy is reduced because it can do less work than before

When the energy of a system changes as a result of a temperaturedifference between it

and its surroundings we say that energy hasbeen transferred as heat.

Exothermic A process that releases energy as heat

~ Example: all combustion reactions are exothermic

Endothermic Process that absorb energy as heat

~ Example: vaporization of water

__________________________________________________________________________
Type of boundary system:

a) Diathermic boundary

b) Adiabatic boundary

A boundary that does permit energy transfer as heat (such as steel and glass) through
its boundary if there is a difference in temperature between the system and its
surroundingsis called diathermic

- A wall is diathermic if a change of state is observed when two objects at

different temperatures are brought into contact. (e.g. a metal container)

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 A boundary that does not permit energy transfer as heat through its boundary even if
there is a temperature difference between the system and its surroundings is
calledadiabatic

A wall is adiabatic if no change occurs even though the two objects have different
temperatures. (e.g. Dewar vessel)

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 Adiabatic
system/container

Diathermic
system/container

a) When an endothermic process occurs in an

adiabatic system, the temperature falls

b) If the process is exothermic, then the temperature rises

c) When an endothermic process occurs in a diathermic container, energy enters as heat from
the surroundings and the system remains at the same temperature

d) If the process is exothermic (diathermic container), then energy leaves as heat and the
process is isothermal

Exercises:

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State true or false for the following questions and explain your answer:

1) A closed system permits the flow of matter across the boundary but does not permit the
flow of energy. (True/false)

2) All combustion reaction release heat to the surrounding. (True/false)

3) Adiabatic system permit energy transfer as heat (such as steel and glass) through its
boundary if there is a difference in temperature between the system and its
surroundings. (True/false)

4) When exothermic reaction occurs, the temperature of the system in diathermic system is
decreases. (True/false)

Learning Outcomes:

After completing this lesson, student will be able to:

a) State, write and explain the zeroth law of thermodynamic

b) State, write and explain the first law of thermodynamic concerning

internal energy, work, heat, state functions, enthalpy, heat capacities,
variation of temperature with enthalpy, ideal gas relationships, isothermal,
adiabatic, reversible and irreversible processes.

1.2 Temperature & the Zeroth Law of Thermodynamics

The zeroth law states that if two systems are each in thermal equilibrium with a third
system, they are also in thermal equilibrium with each other.

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 This law states that if object A is in thermal equilibrium with object B, and object B is in
thermal equilibrium with object C, then object C is also in thermal equilibrium with object
A.

Object in thermodynamic equilibrium have the same temperature

There is a state function, called temperature which has the symbol T, which has the following
relationship to heat, q:

addition of heat to a system will increase the temperature of the system.

Iftwo closed system (together isolated), with different temperatures are brought into
thermal contact, then the temperatures of the two systems will change to approach the
same temperature. That is the temperature of the system which is at a higher
temperature will decrease and the temperature of the system with the lower temperature
will increase. They will eventually have the same temperature.

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 Below you will see two diagrams a set of systems. What is constructed is an isolated
system with two closed systems inside. Initially the two systems are isolated from each
other and are at different temperature. For illustration, in diagram 1 the temperature of
system number 1 is higher than in system 2:

initially: T1> T2

Now we will let the two closed systems come in contact with each other and allow heat
to "flow" from system 1 to system 2. In other words, the walls between the two systems
are not insulating. The zeroth law says then that the flow of the heats will be from
system 1 to system 2. The temperature of system 1 will decrease and the temperature
of system 2 will increase until:

finally: T1 = T2

The First Law of Thermodynamics

The first law of thermodynamics is the law of conservation energy which states that
the energy of the universe is constant which energy can be transffered from the 9
system to its surroundingsor vice versa in any form, heat, potential, kinetic or
electrical energy, but it neither be created nor destroyed.
 Euniverse = Esystem + Esurrounding

or

Uuniverse = Usystem + Usurrounding

Internal energy, U
-Total energy of a system

-total kinetic and potential energy of the molecules composing the system

U = Uf - Ui

The internal energy is a state function in the sense that its value depends only on the
current state of the system and is independent of how that state has been prepared.

Unit for U, w, qare joule (J).Changes in molar internal energy are expressed in kilojoules
per mole (kJ mol-1)

The first law of thermodynamicsstates that the change in the internal energy of a
system is equal to the sum of the heat gained or lost by the system and the work done
by or on the system.

Usystem = q + w

Work done by the

Change in internal system/ work
energy of a system Heat content done on the
(heat gained/lost) system

q (+ve) = heat absorbed by the system

q (-ve) = heat released by the system
w(+ve) = work done on the system
w(-ve) = work done by the system

The internal energy of an isolated system is constant (for which q = 0, w = 0).

Isolated System: A system is said to be isolated system when

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 The system does not have any interaction with the surroundings,
No Heat transfer takes place between the system and surroundings (q = 0)
Work done by the system is zero (w = 0)

Therefore, in case of isolated system, internal energy of the system (Usys) remains
constant and change in internal energy (Usys)of the isolated system is zero.

In a closed system, the change in internal energy (Usys) is equal to the energy that
passes through its boundary as heat or work.

~ whichw> 0 or q > 0 if energy is transferred to the system as work or heat and

w<0 or q<0 if energy is lostfrom the system as work or heat

- energy:
Kinetic

where is the mass and is the speed (or the velocity) of the body.

Mass is measured in kilograms, speed in metres per second, and the resulting kinetic
energy is in joules.

For example, one would calculate the kinetic energy of an 80 kg mass (about 180 lbs)
traveling at 18 metres per second (about 40 mph, or 65 km/h) as:

Ek = (1/2) 80 182 J = 12.96 kJ

where kg is the kilogram, m is the metre, s is the second, N is the newton, Pa is the pascal, W is
the watt, C is the coulomb, and V is the volt.

Exercise:

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1) A gas cools and loses 55 J of heat. The gas contracts as it cools and the work done on
the system equals to 28 J is exchanged with the surroundings. Calculate heat (q), work
(w) and change in internal energy E.

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 is 415 J and the system lost 350 J
of heat to the surrounding. Calculate the energy change in energy, E in kJ

3) If an electric motor produced 15 kJ of energy each second as mechanical work and lost
2 kJ as heat to the surroundings, calculate the change in the internal energy of the motor
each second.

4) When a spring was wound, 100 J of work was done on it, but 15 J escaped to the
surroundings as heat. Calculate the change in internal energy of the spring.

Work and Heat

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 Expansion work the work arising from a change in volume.

a) The general expression of work:

the work required to move an object a distance dzagainst an opposing force F is

dw = -Fdz

-ve = the system moves an object against an opposing force, the internal energy of the
systemdoing the work will decrease

Figure show a piston of area A:

When a piston of area Amoves out through a distance dz, it

sweeps out a volume

dV = A dz

The external pressure, Pexis equivalent to a weight pressing on

the piston and the force opposing expansion (force on the outer
face of the piston)is

F = PexA

When the system expands through a distance dz against an

external pressure, Pex, the work done is

dw = -PexAdz

But A dz is the change of volume, dV, in the course of expansion

Therefore, the work done when the system expands by dV against a pressure Pex is

dw = -PexdV

To obtain the total work done when the volume changes from Vi to Vf, we integrate this
expression between the initial and final volumes:

w=-

w = work (joules (J))

Pex = external pressure (Pa)
dV = change in volume (m3)

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 1J= = N. m = Pa . m3

If the system is expands, Vf> Vi

If the system is compressed, Vf< Vi

b) Free expansion

Free expansion means expansion against zero opposing force, F = PexA

It occurs when Pex = 0

dw = -PexdV

dw = 0 for each stage of expansion. Hence, overall: w = 0

No work is done when a system expands freely

Expansion of this kinds occurs when a system expands into a vacuum

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 The work done by a gas when it expands against a constant
external pressure, Pex, is equal to the shaded area in this
example of an indicator diagram

c) Expansion against constant pressure

Suppose that the external pressure (Pex) is constant throughout

the expansion

For example, the piston may be pressed on by the atmosphere,

which exerts the same pressure throughout the expansion

A chemical example of this condition is the expansion of a gas formed in a chemical

reaction

w = -Pex = -Pex (Vf Vi)

Therefore, if we write the change in volume as V = Vf - Vi

w = -Pex V

d) Reversible expansion:

A reversible change in thermodynamics is a change that can bereversed by an

infinitesimal (value so small to measure them)modification of a variable.

Reversible something that can change direction

~ The system is in equilibrium with its surroundings if an infinitesimal change in the

conditions in opposite directions results in opposite changes in its state

~ Example of reversibility:thermal equilibrium of the 2 systems with the same

temperature. The transfer of energy as heat is reversible because if the T of either
system is lowered infinitesimally, the energy flows into the system with the lower T. If the
T of either system at thermal equilibrium is raised infinitesimally, then energy flows out of
the hotter system

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 To achieve reversible expansion we set pex equal to pat each stageof the expansion. In
practice, this equalization could be achieved bygradually removing weightsfrom the
piston so that the downwardforce due to the weights always matched the changing
upward forcedue to the pressure of the gas.

When pex = p,

pex = external pressure

p = pressure of confined gas

dw = -PexdV = -pdV

The total work of reversible expansion is:

w=-

w = -p V

w = -p (Vf Vi)

e) Isothermal reversible expansion: (of a perfect gas)

Consider the isothermal, reversible expansion of a perfect gas

~ An ideal gas is a theoretical gas composed of many randomly moving point particles
that do not interact except when they collide elastically.

The expansion is made isothermal by keeping the system in thermal contact with its
surroundings (which may be a constant-temperature bath)

The ideal gas equation:

pV = nRT

p = nRT/V (v = volume of the expansion)

R= 8.3145 JK-1mol-1
K = C + 273.15

The work of reversible isothermal expansion of a perfect gas from Vi to Vf at a

temperature T is

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 w = -p dV

w=-

w = - nRT

w = -nRT

w = -nRTln

whenVf>Vi (expansion), w < 0. So, the system has done work on the surroundings and the
internal energy of the system has decreaseas a result of the work it has done.

Calculation:

1) Calculate the work done when 50 g of iron reacts with hydrochloric acid in:

(a) a closed vessel of fixed volume;

(b) an opened beaker at 25 oC.

Answer:

(a) The volume cannot change, so no work is done and w = 0 (dw = -PexdV)

(b) The gas drives back the atmosphere and therefore w = -Pex V. We can neglect the initial
volume because the final volume (after the production of gas) is so much larger and V =Vf Vi
Vf=nRT/Pex, where n is the amount of H2 produced

Therefore:

w = -Pex V -Pex x = -nRT

Because the reaction is

Fe (s) + 2HCl (aq) FeCl2 (aq) + H2 (g)

1 mol Fe 1 mol H2

Molar mass of Fe = 55.85 g/mol

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w=

w = - 2219.3 J

w = -2.2 kJ

~ The system (the reaction mixture) does 2.2 kJ of work driving back to atmosphere

Heat and Enthalpy

In general, the change in internal energy of a system is:

dU = dq + dwexp + dwe

wheredwe = work in addition (e for extra) to the expansionwork, dwexp

For example, dwemight be the electrical work of driving a current through a circuit

A system kept at constant volume can do no expansion work, so dwexp= 0

If the system is also incapable of doing any other kind of work (if it is not, for instance, an
electrochemical cell connected to an electric motor), the dwe= 0 too

dU = dqv (At constant volume, no additional work)

qv= heat at constant volume

For measurable change,

U = qv

U = change in internal energy at constant-volume system

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 q< 0 (the system released energy (heat)

q> 0 (the system obtained/absorbed energy (heat)

(a) Calorimetry

The most common device for measuring U

is the adiabatic bomb calorimeter

Chemical reaction occurinside the constant-

volume container, the bomb

The bomb immersed in a stirred water bath

and the whole device is the calorimeter

The calorimeter is also immersed in an outer

water bath

The water in the calorimeter and that of the

outer bath are both monitored and adjusted to the same temperature

The arrangement ensures that there is no netloss of heat from the calorimeter to
the surroundings (the bath) and hence the calorimeter is adiabatic (no heat enter
or leave the system).

The T is proportional to the heat that the rxn releases or absorbs

q = CT @ C = q/T

The calorimeter constant(C)kJ/K may be measured electrically by passing a

current, I from a source of known electrical potential, through a heater for a

known period of time, t:

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 q =I t

I = current

= electrical potential
t = time

Example:

If we pass a current of 10.0 A from a 12 V supply for 300 s, the heat is

q = (10.0 A) x (12 V) x (300 s) = 3.6 x 104 A V s = 36000J = 36 kJ

because 1 A V s = 1 J

If the observed rise in temperature is 5.5 K, the the calorimeter constant is

C = (36 kJ)/(5.5 K) = 6.5 kJ K-1

Heat capacity

Heat capacity, C is the amount of heat requiredto raise the temperature of a substance
by 1 Kelvin

Specific heat,s is the quantity of heat required to raise the temperature of 1 g substance
by 1 Kelvin.

The internal energy of a substance increases when its temperature is raised. The
increase depends on the conditions under which the heating takes place and for the
present we suppose that the sample is confined to a constant volume.

For example, the sample may be a gas in acontainer of fixed volume. If the internal
energy is plotted against temperature, then a curve like that in Fig. 10 may be obtained.
The slope of the tangent to the curveat any temperature is called the heat capacity of the
system at constant volume at that temperature.

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 *Fig. 10Theinternal energy of a system increasesas the temperature is raised;
this graph shows its variation as the system is heated at constant volume. The
slope of the tangent to the curve at any temperature is the heat capacity at
constant volume at that temperature. Note that, for the system illustrated, the
heat capacity is greater at B than at A.

Physical property of matter are categorized as either Intensive or Extensive property

Heat capacities are extensive properties:

~ e.g.: 100 g of water has 100 times the heat capacity of 1 g of water (and therefore
requires 100 times the energy as heat to bring about the same rise in temperature).

Intensive property (also called a bulk property, intensive quantity, or intensive

variable), is a physical property of a system that does not depend on the system size or
the amount of material in the system.

Macroscopic properties of a system which are independent of mass are known as

intensive properties. Whatever is the mass but properties remain unchanged.
FOR EXAMPLE: COLOUR, ODOUR, CONDUCTIVITY, MELTING POINT, BOILING
POINT, DENSITY, TEMPERATURE, PRESSURE, VISCOSITY.

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 Extensive property (also extensive quantity, extensive variable, or extensive
parameter) is one that is additive for independent, non-interacting subsystems. It is
directly proportional to the amount of material in the system.

Macroscopic properties of a system which are strictly dependent on there mass or

quantity of matter are known as extensive properties.

If mass is halved the property will also be half.

FOR EXAMPLE: volume, mole, mass, enthalpy, internal energy, kinetic energy.

Heat capacity at constant volume, Cv (JK-1)

Molar heat capacityat constant volume, Cv,m(J K-1 mol-1) the heat capacity per mole of
material and is an intensive property (all molar quantities are intensive).

e.g.: CV,mfor polyatomic gases are close to 25 J K1 mol1.

Specific heat capacity (J K-1 g-1) - heat capacity per unit mass. (Usually per gram of
material).

e.g.: CV,sof water at room temperature is close to 4 J K1 g1.

The heat capacity can be used to relate a change in internal energy into a change in
temperature of a constant-volume system:

dU= CvdT(at constant volume)

In general, heat capacities depend on the temperature and heat capacitiesdecrease at

low temperatures.

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 However, over small ranges of temperature at and above room temperature (25C), the
variation is quite small and for approximate calculations heat capacities can be treated
as almost independent of temperature.

If the heat capacity is independent of temperature over the range of temperatures of

interest, then a measurable change of temperature Tbrings about a measurable
increase in internal energy U

U = CvT(at constant volume)

U = qv(at constant volume)

Because a change in internal energy can be identified with the heat supplied at constant
volume, the last equation can be written:

qv = CvT(at constant volume)

~ The relation provides a simple way of measuring the heat capacity of a sample: a
measuredquantity of heat is supplied to the sample (electrically, for example) and the
resulting increased the temperature is monitored- Cv = qv/T

~ The ratio of the heat supplied to the temperature rise it causes is the heat capacity of
the sample

~ A large heat capacityimplies that for a given quantity of heat, there will be only a small
increase in temperature(the sample has a large capacity of heat)

~An infinite heat capacity implies that there will be no increase in temperature however
much heat is supplied. For example:

At a phase transition (such as at the boiling point of H2O),theT of the substance does not
rise as heat is supplied (the energy is used to drive the endothermic phase transition to
vaporize the H2O rather than to increase the temperature), so at the T of a phase
transition, the heat capacity is infinite

Enthalpy

The change in internal energy is not equal to the heat supplied (U q) when the
system is free to change its volume. Under these circumstances some of the energy
supplied as heat to the system is returned to the surroundings as expansion work. So,
dU<dq or U < q

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Fig. 12:When a system is subjected to constant pressure and is free to change its volume,
some of the energy supplied as heat may escape back into the surroundings as work.
The change in internal energy is smaller than the energy supplied as heat.

In this case, the heat supplied is equal to the change in another thermodynamic property
of the system, the enthalpy (H) : q =H

(a) The definition of enthalphy

The enthalphy is defines as

~ Enthalphy (H) is the total heat content of a substance at constant pressure, qp:

H = U + pV H = U + PV

p = pressure of the system

V = volume

A change in enthalpy is equal to the heat supplied at constant pressure to a system.

(The system does no additional work):

dH = dq (at contant pressure, no additional work)

For a measurable change,

H = qp

~ The change in enthalpy = to the energy supplied as heat(at constant pressure)

~ For example: if we supply 36 kJ of energy through an electric heater immersed in an

open beaker of water, then the enthalpy of the water increases by 36 kJ and we write

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 H = +36 kJ

If a process involves only solids or liquids, the values of H and U are almost identical.
Physically, such processes are accompanied byavery small change in volume; the
system does negligible work on the surroundings when the process occurs, so the
energy supplied asheat stays entirely within the system.
H = U + PV

H = U + P V

H+
dH

The enthalpy of a perfect gas:

The enthalpy of a perfect gas is related to its internal energy by using pV = nRT in the
definition of H:

H = U + pV

H = U + nRT

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 This relation implies that the change of enthalpy in a reaction that produces or consumes
gas is

H = U + ngRT(reaction produces or consumes gas)

ng = change in the amount of gas molecules in the rxn

~ For example, in the reaction:

ng = -3 mol

Because 3 mol of gas-phase molecules is replaced by 2 mol of liquid-phase molecules

and at 298 K the enthalpy and internal energy changes taking place in the system are
related by

H = U + ngRT

H - U = ngRT

H U= (-3 mol) x RT -7.5 kJ

~ The difference is expressed in kilojoules, not joules

~ The H (enthalpy) <U(the change in internal energy) because although heat escapes
from the system when the rxn occurs, the system contracts when the liquid is formed, so
the energy is restored to it from the surroundings.

The variation of enthalpy with temperature

The enthalpy of a substance increases as its temperature is raised.The relation between

the increase in enthalpy and the increase in temperature depends on the conditions (for
example, constant pressure or constant volume).

The most important condition is constant pressure, and the slope of the tangent to a plot
of enthalpy against temperature at constant pressure is called the heat capacity at
constant pressure(Cp) at a given temperature.

Continue

Heat Capacity at Constant Pressure (Cp) vs Heat Capacity at Constant Volume (Cv)

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 The slope of a graph of the enthalpy of a system subjected to a constant pressure
plotted against T is the heat capacity at constant pressure

The slope of the graph may change with T, in which case the heat capacity varies with T.
Thus, the heat capacities at A and B are different

For gases, the slope of the graph of enthalpy versus T is steeperthan that of the graph of
internal energyversus T and Cp,mis larger than Cv,m(Cp,m>Cv,m)

Heat capacity at constant pressure, Cp,

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 Molar heat capacity at constant pressure, Cp,m(J K-1 mol-1) the heat capacity per mole of
material.

Specific heat capacity (J K-1 g-1) - heat capacity per unit mass. (Usually per gram of
material)

The heat capacity at constant pressure is used to relate the change inenthalpy to a
change in temperature. For infinitesimal changes oftemperature,

dH = CpdT (at constant pressure)

If the heat capacity (constant) is independent of temperature over the range

oftemperatures of interest, then a measurable change of temperatureTbrings about a
measurable increase in H

H = CpT(at constant pressure)

H = qp

Because an increase in enthalpy can be equated with the heat supplied at constant
pressure,

qp = CpdT(at constant pressure) @ Cp = qp/T

~ This expression shows how to measure the heat capacity of a sample: a measured
quantity of heat is supplied under conditions of constant pressure (as in a sample
exposed to the atmosphere and free to expand) and the temperature rise is monitored.

In general, heat capacities depend on the temperature and heat capacities decrease at
low temperatures.

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 However, over small ranges of temperature at and above room temperature (25C), the
variation is quite small and for approximate calculations heat capacities can be treated
as almost independent of temperature

The variations of heat capacity with temperature can sometimes beignored if the
temperature range is small(at and above room temperature (25C)); this approximation
is highlyaccurate for a monatomic perfect gas (for instance, one of the noblegases at low
pressure). However, when it is necessary to take thevariation into account, a convenient
approximate empirical expressionis

~ The empirical parameters a, b, and c are independent of temperature.

Temperature variation of molar heat capacities, Cp,m/(JK-1mol-1) = a + bT + c/T2

(d) The relation between heat capacities

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 Most systems expand when heated at constant pressure. Such systems do work on the
surroundings and therefore some of the energy supplied to them as heat escapes back
to the surroundings.As a result, the temperature of the system risesless when the
heating occurs at constant pressure.

A smaller increase in temperature implies a larger heat capacity, so we conclude that in

most cases the heat capacity at constant pressure of a system is larger than its heat
capacity at constant volume(Cp>Cv).

Simple relation between the two heat capacities of a perfect gas:

At constant pressure:

Cp>Cv

Cp - Cv = nR

Cp,m - Cv,m = R

v
Cp - Cv =

H = U + PV = U + nRT

Cp - Cv =

Cp - Cv = nR

Example:

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Evaluating an increase in enthalpy (H) with temperature (T)

What is the change in molar enthalpy of N2when it is heated from 25C to 100C? Use the heat
capacity information in Table 2.2.

Solution:

dH = CpdT

dH,m = Cp,mx n x dT

H (373 K) H (298 K) =

H = 2204.626 Jmol-1
= 2.20 kJmol-1

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Adiabatic changes

Changes that occur when a perfect gas expands adiabatically is discussed.

A decrease in temperature should be expected: because work is done but no heat enters
the system, the internal energy falls, and therefore the temperature of the working gas
also falls. In molecular terms, the kinetic energy of the molecules falls as work is done,
so their average speed decreases, and hence the temperature falls.

The figure on the right is incorrect for a reversible adiabatic expansion, since the
temperature must drop during an expansion.

i f

WhenV increases, T decreases during adiabatically expansion

Fig. 14 To achieve a change of state from one temperature andvolume to another

temperature and volume, we may consider the overall change as composed of
two steps. In the first step, the system expands at constant temperature; there is
no change in internal energy if the system consists of a perfect gas. In the
second step, the temperature of the system is reduced at constant volume. The
overallchange in internal energy is the sum of the changes for the two steps.

The change in internal energy of a perfect gas when the temperature is changed from Ti
to Tf and the volume is changed from Vi to Vfcan be expressed as the sum of two steps
(Fig. 14).

First step:

The volume changes and the temperature is held constant at its initial value

Second step:

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 The change in temperature at constant volume
Because the internal energy of a perfect gas arises solely from the kinetic energies of
the molecules, the overall change in internal energy arises solely from the 2nd step
The heat capacity is independent of temperature, this change is:

U = Cv(Tf Ti) = CvT

Because the expansion is adiabatic: q = 0

U =q+w
Justification
U
The=expansion
wad is reversible, so the internal and external pressures are equal
wThe
ad = CvT
work done when the gas expands by dV: w = -pdV

However, for perfect gas: dU = CvdT

wad T (The work done during an adiabatic expansion of a perfect gas is proportional
to the temperature difference
Adiabatic change: dU = dw between initial and final states)

CvdT = -pdV
Kinetic energy is proportional to T, so change in internal energy arising from the
Perfect gas: is
temperature replace p = nRT/V to T
also proportional

The most important type of adiabatic expansion is reversible adiabatic expansion, in

CvdT =external
which - dV
pressure is matched to the internal pressure.

The initial and final temperatures of a perfect gas that undergoes reversible adiabatic
expansion:
Cv = -nR

VfTfc = ViTic c=
Cv = -nR
This expression is derived in the following justification

Cv is independent of T. Then, because , we obtain

Tf = Ti

calculate
Cvln T and substitute into equation wad = CvT to find work done by the system
= -nRln

ln = -ln

With c = Cv/nR and by using a ln x = lnxa and ln(x/y) = ln (y/x)

33

ln = ln
Problem:

34
Consider the adiabatic, reversible expansionof 0.020 molAr, initially at 25C, from 0.50 dm 3 to
1.00 dm3. The molar heat capacity of argon at constant volume is 12.48 J K 1 mol1, what is the
work done?

Solution:

Mol = 0.020 molAr

Ti = 25C (25 + 273.15 K = 298.15 K)

Vi = 0.50 dm3

Vf =1.00 dm3

Cv,m = 12.48 J K1 mol1

Tf = Ti

c=

c=

c = 1.501

Tf = 298.15 K
Tf = 187.88 K

wad = CvT

wad = Cv(Tf Ti)

wad = n x Cv,m(Tf Ti)

wad =12.48 J K1 mol1x0.020 mol x (187.88 K - 298.15 K)

wad = -27.5 J

35
Heat Capacity Ratio and Adiabats

The change in pressure results from the adiabatic, reversible expansion of a perfect gas

pV = constant

where the heat capacity ratio, , of a substance is defined asratio of the molar heat
capacity at constant pressure (Cp,m) to molar heat capacity at constant volume (Cv,m).

Because the heat capacity at constant pressureisgreater than the heat capacity at

constant volume (Cp,m>Cv,m), . For a perfect gas, it follows from equation Cp - Cv =

nR orCp,m - Cv,m = Rthat

~ For monoatomic perfect gas, Cv,m = R, so = = 1.667

~ For a gas of nonlinear polyatomic molecules, Cv,m= 3R, so = 1.333

36
 The change in pressure of a perfect gas that undergoes reversible adiabatic expansion
pressure from a volume Vi to a volume Vfis related to its initial by:

Justification:

Perfect gas law: PV = nRT

For a reversible adiabatic change, the temperature change is

orTf = Ti

or or

Then, combine the two expressions to obtain

or,

37

It follows that pV = constant

 The curves of pressure versus volume for adiabatic change are known as adiabats, and
one for a reversible path is illustrated in Fig. 15. Because > 1, an adiabat falls more
steeply (P 1/V) than the corresponding isotherm (P 1/V).

The physical reason for the difference is that, in an isothermal expansion, energy flows
into the system as heat and maintains the temperature; as a result, the pressure does
not fall as much as in an adiabatic expansion.

Fig. 15: An adiabat depicts the variation of pressure with volume when a gas expands
reversibly and adiabatically. (a) Adiabat for a perfect gas. (b) The pressure declinesmore
steeply for an adiabat than it does for an isotherm because the T decreases in the
former

Problem :

When a sample of argon (for which = 5/3) at 100 kPa expands reversibly and adiabatically to
twice its initial volume, what is the final pressure?

38
Solution:

= (100 kPa) x = 31.5 kPa

The Second Law

Some things happen naturally; some things dont.

Thermodynamics is silent on the rate at which a spontaneous gas change in fact occurs,
and some spontaneous processes (such as the conversion of diamond to graphite) may
be so slow that the tendency is never realized in practice whereas others (such as the
expansion of a into a vacuum) are almost instantaneous.

Spontaneous changes are always accompanied by a dispersal of energy.

~ the role of the distribution of energy can be illustrated by thinking about a ball (the
system of interest) bouncing on a floor (the surroundings)

~ the ball does not riseas high after each bounce because there
are inelastic losses in the materials of the balland floor (that is, the
conversion of kinetic energy of the balls overall motion into the
energy of thermal motion)

~ On each bounce some of its energy is degraded into the thermal

motion of the atoms of the floor and that energy disperses

Two classes of process: spontaneous and non-spontaneous is summarized by second

law of thermodynamic

One statement was formulated by Kelvin: No process is

possible in which the sole result is the absorption of heat
from a reservoir and its complete conversion into work.

~ For example, it has proved impossible to construct an engine

like figure below in which heat is drawn from a hot reservoir and
completely converted into work

~ All real heat engines have both of a hot source and a cold sink
and some heat is always discarded into the cold sink and not
converted into work

39
Spontaneity and entropy

Entropy, S is defined as the measure of the degree of molecular disorder or randomness

in a system

- Entropy is an expression of disorder or randomness

Spontaneous process favoured by decrease in enthalpy (H<0) @ H (-ve)

- favoured by increase in entropy (S>0) @ S (+ve)

But, not all spontaneous processes are exothermic. Why?? Third law of thermodynamic

Increase in disorder or randomness value of S increase, S > 0 (S = +ve)

Less disorderor less randomness value of S decrease (S = -ve)

The total change in entropy,Stotal

Stotal = Ssystem+ Ssurrounding

If Stotal> 0, the process is spontaneous

If Stotal< 0, the process is nonspontaneous

If Stotal = 0, the process is at equilibrium

The second law of thermodynamics states that the total entropy of the system and its
surroundingin a closed isolated system is always increases in every spontaneous process

The second law of thermodynamics can be expressed in terms of the entropy:

40
 ~ The entropy of an isolated system (dq = 0, dw = 0)increases in the course of
aspontaneous change:

Stot> 0

Stot= the total entropy of the system and its surroundings

~ Thermodynamically irreversible processes (like cooling to the temperature of the

surroundings and the free expansion of gases) are spontaneous processes, and hence
must be accompanied by an increase in total entropy.

The simplest way to state the second law is for an isolated system.

This is a system for which dq = 0, and dw = 0.

S=0forareversiblechange

S>0foranirreversiblechange
~ S < 0 is impossible for an isolated system

The following factors increase the entropy of a system:

a) Change in state from solid to liquid

b) Change in state from liquid to gas
c) Change in state from solid to gas
d) Formation of a mixture
e) Increase in volume of the gases system
f) Adding heat to the system

- Spontaneous reactions lead to increase in entropy. Spontaneous process

reduces the state of order of the initial systems to become more disorder.

Example: Water molecules are arranged orderly in crystal lattice in ice but the
structure deforms as ice melts to give less order molecular rearrangement.

There are 2 main types of thermodynamic process:

a) Reversible process

- Process that proceed one direction to another which is spontaneous

- Known as equilibrium process

41
b) Irreversible process

- Process which both system and surrounding cannot return to the original condition.

-The system is not at equilibrium

Spontaneous process vs non-spontaneous process

~Spontaneous process or change including chemical reactions is one that occurs on its own
without external interferences or influences.

Example:

a) Heat flows form hot object to cold object is spontaneous

b) Consider a gas placed in a bulb A & joined to another evacuated bulb B by a stopcock.

- Initially gas only occupies bulb A

- When stopcock is opened, gas in bulb A expands spontaneously to occupy

bulb B until the pressure in both bulbs is the same

- Therefore, spontaneous processfavors the increase in disorder or randomness

of the molecules

- Since the number of gas molecules decreases in bulb A, the kinetic energy
increases & the molecules become more disorder.

- The molecules occupying bulb B also have more kinetic energy after escaping
form bulb A and become disorder as well

- Hence, the entropy of the gas also increases.

- However, evacuating the gas from bulb B to bulb A is nonspontaneous.

42
 - Compressing gas molecules from larger to small volume reduces the kinetic
energy, the molecules become less disorder.

- Therefore, the entropy of the system decreases.

The thermodynamic definition of entropy

Thermodynamic definition of entropy concentrates on the change in entropy, dS, that

occurs as a result of a physical or chemical change (in general, as a result of a
process).

A change in the extent to which energy is dispersed depends on how much energy is
transferred as heat.

Heat stimulates random motion in the surroundings (increase in entropy). On the other
hand, work stimulatesuniform motion of atoms in the surroundings and so does not
change their entropy.

The thermodynamic definition of entropy (at constant T) is based on the expression

At constant T (example: melting, boiling point (equilibrium)

S = qrev/T

For a measurable change between two states i and f this expressionintegrates to

To calculate the difference in entropy between any two states of a system, a reversible
path between them is adopted. Integrate the energy supplied as heat at each stage of
the path divided by the temperature at which heating occurs.

q = Joule

T=K

S = JK-1

Molar entropy = ; JK-1mol-1

At constant pressure:

43
qrev = H

S = qrev/T

S = H/T
T = H/S
Example:

Calculate the entropy change of a sample of perfect gas when it expands isothermally from a
volume Vi to Vf.

Answer:

~ Expansion is isothermal, so the T is a constant (may be taken outside the integral in eqn:

~ The heat absorbed during a reversible isothermal expansion of a perfect gas can be
calculated from

U = q + w

U = 0

q = -w

therefore, for a reversible change

qrev = -wrev

The work of reversible isothermal expansion:

w = -nRTln

Answer:

Because the T is constant, eqn becomes

S =

44
qrev = -wrev= nRTln

Therefore, it follows that: S =nRln

Example: when the volume of 1.00 mol of any perfect gas is doubled at any constant
temperature:

S =nRln

S = (1.00 mol) x (8.3145 JK-1mol-1) x ln 2 = +5.76 JK-1

Exercise:

Calculate the change in entropy when the pressure of a perfect gas is changed isothermally
from pi to pf

Answer:

PV = nRT

P=

S =

The work of reversible isothermal expansion:

w = -nRTln

qrev = -wrev= nRTln

45
S = nRln or -nRln

Consider an infinitesimal transfer of heatdqsurto the surroundings.Thesurroundingsconsist

of a reservoir of constant volume, so the energy supplied to them by heating can be
identified with the change in their internal energy, dUsur.

The internal energy is a state function, and dUsuris an exact differential. So, dUsur is
independent of how the change is brought about and in particular is independent of
whether the process is reversible or irreversible.

dSsur=

~ Because the T of the surroundings is constant whatever the change, for a measurable
change

Ssur =

~ For any adiabatic change:

qsur = 0, so

Ssur = 0

~ There are change takes place: reversible & irreversibly

When a chemical reaction takes place in a system in thermal equilibrium with its
surroundings (Tsur = T),

Ssur =

46
Justification:

47
Calculation:

Calculate the entropy changeinthesurroundings when 1 mol of H2O (l) is formed from its
elements under standard conditions at 298.15K. (given that :Hf (H2O, l) = - 286 kJ)

Answer:

n = 1 molH2O

T = 298.15K

Hf =- 286 kJ

The heat released is supplied to the surroundings at constant pressure :dqrev = dHrev,

qsur = -qrev

Soqsur = +286 kJ

At constant pressure: qrev = H

qsur, rev = H

qsur = H

Ssur =

48
Ssur =

The statistical view of entropy

Entropy is the degree of disorder in a system.

The perfectly ordered system has zero entropy.

The less perfectly ordered system has higher entropy.

The expansion of perfect gas/ Reversible Isothermal Expansion

The change in entropy of a perfect gas that expands isothermallyformVi to Vf is

Because S is a state function, the value of S of the system is independent of the path
between the initial and final states, so this expression applies whether the change of
state occurs reversibly or irreversibly.

The total change in entropy, however, does depend on how the expansion takes place.
For any process dqsur = dq, and for a reversible change:

49
 Stotal = Ssystem+ Ssurrounding

qrev = nRTln

S =

Isothermal expansion occurs freely (w = 0) and irreversibly

The total change in entropy depends on how the expansions take places.
If the change is reversible:
Stot = 0

Ssur = -nRln (-ve),

Stotal = Ssystem+ Ssurrounding

If the gas expands freely into a vacuum: dw = 0, dq = 0

If the expansion occurs freely(w = 0) and irreversibly, and if the T remains constant, then

q = 0 (U = 0)

Ssur =qsur/T

50
 Ssur = 0 (no heat transfer into the surroundings)

The total entropy change if the expansionoccursfreelyandirreversibly is given by eqn:

Stotal = Ssystem+ Ssurrounding

Stot = nRln +0

Stot = nRln
Stot> 0

Irreversible Isothermal Expansion

dU = 0(T constant)

dU = dq + dw

dq = -dw

The entropy of phase transition (trsS)at the transition temperature (Ttrs)

A change in the degree of molecular order occurs when a substancefreezes or boils, we

should expect the transition to be accompanied by a change in entropy.

e.g.

a) when a substance vaporizes, a compact condensed phase changes into a widely

dispersed gas. So, the entropy of the substance increases.

b) The entropy of a solid substanceincreases when it melts to liquid and it also increases
when the liquid turns into gas

Consider a system & surroundings at the normal transition temperature, Ttrs = the T at
which 2 phases are in equilibrium at 1 atm

At the transition T, any transfer of heat between the system & the surroundings is
reversible because the 2 phases in the system are in equilibrium

A phase transitionat the transition temperature under 1 atm pressure is a reversible

isothermal process (constant pressure). Because at constant pressure, q = trsH
(change in transition enthalpy), the entropy change of the system:

51
 e.g.

Transition T, Ttrs is:

1) at 273 K (0 oC) for ice in equilibrium with water at 1 atm

2) at 373 K (100 oC) for water in equilibrium with its vapor at 1 atm

If the phase transition is exothermic (freezing & condensing) : trsH< 0, S is ve

~ this decrease in entropy is consistent with the system becoming more ordered when a
solid forms from a liquid (freezing)

If the phase transition is endothermic (melting & vaporizing) : trsH> 0, S is +ve

~ this increase in entropy is consistent with the liquids being more disordered than solids
(melting)&gases more disordered than liquids (vaporization/boiling/evaporation)

Some experimental entropies of transition are listed in the table 4.1:

Tb =
normal boiling
point of T
Tf = melting point
Fusion : entropy when melting a substance

The standard entropies of vaporization of several liquids at their boiling points are listed
in table 4.2:

52
~ An interesting feature of the data is that a wide range of liquids give approximately the same
standard entropy of vaporization (about 85 JK -1mol-1). This empirical observation is called
Troutons rule.

What is Troutons rule?

~The value vapS is approximately the same (and equal to about 85 JK-1mol-1)for all liquids
except when hydrogen bonding or some other kinds of specific molecular interaction is present.

~ vapS is the entropy of vaporization of the liquid at its boiling point, so Troutons rule explained
if all liquids have approximately the same entropy of vaporization at their boiling point.

vapS = vapH/Tb

Why liquids have same value of standard entropy of vaporization (about 85 JK-1mol-1)?

A comparable amount of disorder is generated when any liquid evaporates and becomes
a gas. Hence, all liquids can be expected to have similar standard entropies of
vaporization.

This near equality is to be expected because when a liquid vaporizes, the compact
condensed phase changes into a widely dispersed gas that occupies approximately the
same volume whatever its identity.

To a good approximation, therefore we expected the increase in disorder& therefore the

entropy of vaporization to be almost the same for all liquids at their boiling temperature.

53
 Liquid that show significant deviation from Troutons rule molecules in the liquid being
arranged in a partially orderly manner

The exceptions to Troutons rule include liquids in which the interactions between
molecules result in liquid being less disordered than a random jumble of molecules.

For example, the high vapS value for water implies that the water molecules are linked
together in some kind of ordered structure by hydrogen bonding with the result that the
entropy change is greater when this relatively ordered liquid forms a disordered gas.

A greater change of disorder occurs when the liquids evaporates than if the molecules
were highly disordered in the liquid

54
 Example: a large entropy of vaporization reflects the presence of structure arising from
hydrogen-bonding in the liquid. Hydrogen bonds tend to organize the molecules in the
liquidin partially orderly manner so that they are less random than for example, the
molecules in liquid hydrogen sulfide (which are not hydrogen bonded)

The variation of entropy with temperature

Calculate the entropy of a system(S) at a temperature Tffrom its entropy at a

temperature Tiand the heat supplied to change its temperature from one value to the
other:

Ssys = S(Tf) S(Ti)

S(Tf) = S(Ti)+ Ssys

S(Tf) = S(Ti) +

55
 S at constant pressure during the heating:

dqp= dqrev = CpdT

so as long as the system isdoing no non-expansion work. Consequently, at constant

pressure:

S(Tf) = S(Ti) +

S(Tf) = S(Ti) +

S(Tf) = S(Ti) + Cp

S = Cp or S = n x Cp,m

S at at constant volume:

dU = dqv = dqrev

dU = CvdT

S(Tf) = S(Ti) +

S(Tf) = S(Ti) +

S(Tf) = S(Ti) +

S(Tf) = S(Ti) + Cv

56
 S =Cv or S =n x Cv,m

___________________________________________________________________________

V1 V2
If volume change occurs in ideal gas with a change in T, what is Ssys?
T1 T2

dU = dq + dw

dU = dqrev+ (-pdV)

dqrev = dU + pdV

= CvdT +

dqrev = nCv,mdT+

dS = =

S = nCv,m

T1 T2
If pressure change occur in ideal gas with a change in T, what is the

57
P1 P2
Ssys?

2nd Law of Thermodynamics: Differential form: dS =

H = U + PVordH = dU + pdV or H = U + pV

H + dH = (U + dU) + (p + dp)(V + dV)

H + dH = U + dU + pV +pdV + Vdp + dpdV

U + pV = H

H + dH = dU + H +pdV + Vdp

dH = dU +pdV + Vdp

At constant volume: pdV = 0

dH = dU + Vdp

dqv = dU (at constant volume)

dH = dq + Vdp

1st Law for a gas :dq =dH - Vdp

Ideal gas : dH = CpdT

Substitute :dq=CpdT -

dS =

Substitute :dS =

Integrate :S2 S1 =

58
Specific form :S =

Example:

Calculate the entropy change when argon at 25 C and 1.00 atm in a container of volume 500
cm3 is allowed to expand to 1000 cm3and is simultaneously heated to 100 C. (Cv,m = 12.47 JK-1
mol-1)

Answer:
R with different units:

S? 8.31451JK-1mol-1

Ti= 25 C (25 + 273.15 = 298.15 K) 8.20578 x 10-2L atm K-1mol-1

Tf = 100 C (100 + 273.15 = 373.15 K) 8.31451 x 10-2L bar K-1mol-1

Vi = 500 cm3 8.31451 Pa m3 K-1mol-1

Vf= 1000 cm3 62.364 LTorr K-1mol-1

p = 1 atm 1.98722 cal K-1mol-1

Cv,m = 12.47 JK-1 mol-1

First step:Reversibleisothermal expansion to the final volume

PV = nRT

n=

n = 0.0204 mol

The entropy change in the first step (expansion from 500 cm3 to 1000 cm3 at 298 K) is:

59
S = 0.0204 mol x 8.314 JK-1mol-1 x ln

S = 0.118 JK-1

Secondstep:Reversibleheating at constant volume to the final temperature

The entropy change from 298 K to 373 K at constant volume is:

S = nCv,mdT

S =nCv,mln

= 0.0204 mol x 12.47JK-1 mol-1 x ln

= 0.057 JK-1

The overall entropy change, the sum of these two changes:

S = S1 + S2

S = 0.118 JK-1 + 0.057 JK-1

= 0.175 JK-1

60
Third Law

At T = 0 K, all energy of thermal motion has been quenched (suppress/minimum energy

state), and all the atoms or ions are in a regular, uniform array in a perfect crystal.

~ Thermal Energy, also known as random or internal Kinetic Energy, due to the random
motion of molecules in a system.

~ Thermal energy is the part of the total potential energy and kinetic energy of an object
or sample of matter that results in the system temperature

The localization of matter and the absence of thermal motion suggest that such
materials also have zero entropy.

S = 0 if there is only one way of arranging the molecules (the ground state).

The third law of thermodynamics is stated as follows, regarding the properties of

systems in equilibrium at absolute zero temperature:

~ The entropy of a perfect crystal, at absolute zero kelvin, is exactly equal to zero.

~ The entropy changes become zero at absolute zero provided that the states of the
system are in thermodynamic equilibrium.

Absolute zero is the lower limit of the thermodynamic temperature scale

~Absolute zero is defined to be 273.15C, or 0 K.

Perfect crystal is a crystal with no defects or impurities and made of

repeating identical subunits with only one possible arrangement.

(a) The Nernst Heat Theorem

The thermodynamic observation that turns out to be consistent with the view that the
entropy of a regular array of molecules is zero at T = 0 is known as the Nernst heat
theorem:

The entropy change accompanying any physical or chemical transformation

approaches zero as the temperature approaches zero : S 0 as T 0 provided all
the substances involved are perfectly crystalline.

61
 If the value zero to the entropies of elements in their perfect crystalline form at T = 0 is
ascribed, then all perfect crystalline compounds also have zero entropy at T = 0.

~ because the change in entropy that accompanies the formation of the compounds, like
the entropy of all transformations at that T, is zero

S of regular array of molecule = 0 at T = 0

Third Law of Thermodynamics:

The entropy of all perfect crystalline substances is zero at T = 0.

This conclusion is summarized by the third law of thermodynamics:

~ If the entropy of every element in its most stable state at T = 0 is taken as zero,
then every substance has a +ve entropy which at T = 0 may become zero, and
which does become zero for all perfect crystalline substances including
compounds

It should also noted that the Third Law does not state that entropies are zero at T = 0: it
merely implies that all perfect materials have the same entropy at that T

As far as thermodynamics is concerned, choosing this common value as zero is then a

matter of convenience. (S = 0 at T = 0)

62
Third-Law entropies

S(0) = 0 --- for all perfect crystals (Third-Law entropies or just standard entropies)

denotes standard (Third-Law) entropy when the substance is in its standard state
at the temperature T.

A list of values at 298 K is given in Table 4.3:

Standard molar entropy is the entropy content of one

mole of substance, under standard conditions.

The standard reaction entropy is defined as the difference between the molar
entropies of the pure, separated products and the pure, separated reactants, all
substances being in their standard states at the specified temperature:

In this expression, each term is weighted by the appropriate stoichiometric coefficient.

63
 nJ = stoichiometry no. in chemical equation

Example:

2A + B 3C + D, calculate rS?

rS =

Calculation

Calculate the standard entropy of H2 (g) + O2 (g) H2O (l) at 25 C.

Given:

S (H2,g) = 130.7 JK-1mol-1

S (O2,g) = 205.0 JK-1mol-1
S (H2O,l) = 69.9 JK-1mol-1
S (H2O,g) = 188.83 JK-1mol-1

Answer:

rS =

= 69.9 {130.7+(205.0)} JK-1mol-1

rS = -163.3 JK-1mol-1

The negative value is consistent with the conversion of two gases to a compact liquid

64
The Helmholtz* (A)and Gibbs energies (G)

Consider a system in thermal equilibrium with its surroundings at a temperature T.

The condition for equilibrium therefore:

dStotal = dSsystem+ dSsurr

~ Suppose that the system and the surroundings are at the same temperature

Tsys = T surr
~ Suppose that a process occurs spontaneously in the system and that an amount of
heat dq leaves the system and enters the surroundings. This amount entering the
surroundings may be written as dqsurr and it is equal to the heat change dq sys in the
system:

dqsurr = -dqsys

dq = dq = dU

The entropy change in the surroundings is

dSsurr =

butTsurr = Tsys and dqsurr = -dqsys, therefore

dSsurr =

Therefore, the equilibrium conditions write as:

dStotal = dSsys - =0

The condition for equilibrium can be written simplify (by drop the superscript sys) as

65
 dS - (the process is at equilibrium)

Alternatively, we can write

dq TdS = 0(the process is at equilibrium)

The Clausius Inequality

dStot 0 for any spontaneous change

If the process is irreversible, the total entropy will increase when a process occurs in the
system. So we can write

dS + dSsur 0, or dS -dSsur (The equality also applies if the process is reversible)

dqsur = -dq(because the heat that enters the system comes from the surroundings)

dSsur = -dq/T, (where dq is the heat supplied to the system during the process)

dS

This expression is called Clausius Inequality

Suppose the system is isolated from its surroundings. The dq = 0 and the Clausius
inequality implies that

dS 0

Suppose a system undergoes an irreversible adiabatic change:

- Then dq = 0 and dS 0 (for this type of spontaneous change, the entropy of

the system has increased)
- Because no heat flows into the surroundings, their entropy remains constant
and dSsur = 0.

66
 - Therefore, the total entropy of the system & the surroundings obeys dStot 0

Consider irreversible isothermal expansion of a perfect gas:

- dq = -dw (because dU = 0)

Free expansion:

- If the gas expands freely into a vacuum, it does no work and dw = 0, dq = 0.

Therefore according to the Clausius inequality, dS 0

- No heat transfer to the surroundings, so dSsur = 0. Therefore, dStot 0

When a change in the system occurs and there is a transfer of energy as heat between
the system and the surroundings, the Clausius inequality, equation reads

dSsur = -dq/T, where dq is the heat supplied to the system during the process (that is, dqsur =
-dq, because the heat enters the system comes from the surroundings

Criteria for spontaneity

The inequality can be developed in 2 ways according to the conditions (of constant
volume or constant pressure) under which the process occurs

Consider heating at constant volume and in the absence of non expansion work

dS -

TdS dU or dU T dS 0

67
Note: additional work is work other than expansion work

At either constant internal energy (dU= 0) or constant entropy (dS= 0), this expression
becomes, respectively:

Equation above expresses the criteria for spontaneous change in terms of properties
relating to the system

Interpretations:

1. The first inequality states that, in a system at constant volume and constant
internal energy (such as an isolated system), the entropy increases in a spontaneous change.

2. The second inequality states that, if the entropy and volume of the system
are constant, then the internal energy must decrease in a spontaneous change.
___________________________________________________________
When energy is transferred as heat at constant pressure, and there is no work other
than expansion work:

dS -

TdS dH or dH TdS 0

68
 At either constant enthalpy (dH= 0) or constant entropy (dS= 0), this inequality becomes,
respectively:

Interpretations:

1. The first inequality dSH,P 0 states that the entropy of the system must increase if its enthalpy
remains constant (for there can be no change in entropy of the surroundings).

2. The second inequality dHS.P 0 states that the enthalpy must decrease if the entropy of the
system is constant, for then it is essential to have an increase in entropy of the surroundings

Because eqn dU TdS 0 and dH TdS 0, respectively, the can be expressed more
simply by introducing 2 more thermodynamic quantities.

Helmholtz energy* (A) which is defined as a thermodynamic potential that measures the
useful work obtainable from a closed thermodynamic system at a constant temperature and
volume.

Gibbs energy (G)

The Gibbs free energy (SI units J/mol) is the maximum amount of non-expansion work that can
be extracted from a closed system, this maximum can be attained only in a completely
reversible process.

When the state of the system changes at constant temperature, the two functions
change as follows:

dA = dU TdS(if the change is infinitesimal)*

69
 A = U TS (if it is measurable)*

and

dG = dH TdS(if the change is infinitesimal)

G = H TS (if it is measurable)

So, the criteria of spontaneous change (for system changes at constant temperature) as

Or dU TdS 0 (heating occur at constant volume)

Or dH TdS 0 (heating occur at constant pressure)

These inequalities are the most important conclusions from thermodynamics for chemistry.

Some remarks on the Gibbs energy

The Gibbs energy (the free energy) is more common in chemistry than the Helmholtz
energy because more interest in changes occurring at constant pressure than at
constant volume.

The criterion is spontaneous in the direction of decreasing Gibbs energy

at constant T and pressure.

If G decreases as the reaction proceeds, then the reaction has a spontaneous tendency
to convert the reactants into products. If G increases, then the reverse reaction is
spontaneous.

Spontaneous endothermic reactions:

dS> 0

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 The entropy of the system increases so much that TdS outweighs dH in dG= dH TdS.

Endothermic reactions are therefore driven by the increase of entropy of the system, and
this entropy change overcomes the reduction of entropy brought about in the
surroundings by the inflow of heat into the system (dSsur = dH/T at constant pressure).

Endothermic: H> 0 (+ve), S is +ve

dG =dH - TdS

G = H TS

If H (+ve) &S (+ve):

G < 0 (-ve): Spontaneous at high T

G > 0 (+ve) :Nonspontaneous at low T

Spontaneous Exothermic: H < 0 (-ve), S is +ve

G = H TS

If H (-ve) &S (+ve):

G < 0 (-ve): Spontaneous at all T

The effect of temperature on spontaneity:

H S G = H TS Spontaneity
-ve +ve -ve Spontaneous at all T

+ve -ve +ve Nonspontaneous at all T

-ve -ve -ve or +ve Spontaneous at low T,

nonspontaneous at high T

+ve +ve -ve or +ve Spontaneous at high T,

nonspontaneous at low T

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Why are all spontaneous processes not exothermic?

All spontaneous processes are not exothermic, because it is the Gibbs Free energy that
determines spontaneity, not the enthalpy.

A process is spontaneous if the Gibbs free energy is negative. An important expression for the
Gibbs free energy is given by
G=HTS
Where S is the change in entropy and T is the absolute temperature in K.

You will notice that this expression may be positive even with a negative enthalpy change
(exothermic process) if the entropy change is negative and the temperature is high enough.

Standard molar Gibbs energy of reaction

Standard entropies & enthalpies of rxn can be combined to obtain the standard Gibbs

energy of rxn, (or standard reaction Gibbs energy):

rG = rH -TrS

or

S
The standard of Gibbs free energy of rxn is difference in standard molar Gibbs
energies of the products & reactants in their standard states at the T specified for the rxn
as written

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 As in the case of standard rxn enthalpies, it is convenient to define the standard Gibbs

energies of formation, fG :

The standard Gibbs energy of formation is the standard reaction Gibbs energy for
the formation of a compound from its elements in their references state

Standard Gibbs energies of formation of the elements in their reference states are zero,
because their formation is null rxn

The standard Gibbs energy of rxn can be calculated from:

Calculation

Calculate the standard reaction Gibbs energy for

CO (g) + O2 (g) CO2 (g) at 25 C.

Given:

G(CO,g) = -137.2 kJmol-1

G(O2,g) = 0 kJmol-1
G(CO2,aq) = -385.98 kJmol-1
G(CO2,g) = -394.4 kJmol-1

Answer:

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 = -394.4 {(-137.2 + (0)} kJmol-1

= -257.2 kJmol-1

Calorimetry (for H directly and for S via heat capacities) is only one of the ways of

determining the values of Gibbs energies

S =Cv

Standard Enthalpy Changes, H

Enthalpy change, H is the amount of heat evolved or absorbed in a reaction carried

out at constant pressure.

Standard enthalpy changes refer to reactions done under standard conditions, and
with everything present in their standard states. Standard states are sometimes referred
to as "reference states"

Standard conditions are:

- 298 K (25C)

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 - a pressure of 1 bar (100 kPa) / 1 atm (1 bar = 0.99 atm)
- where solutions are involved, a concentration of 1 mol dm -3

Standard enthalpy change, H measure amount of heat evolved or absorbed which

reaction occurs under standard conditions

Example of a standard enthalpy change:

a) Standard enthalpy of vaporization, - the enthalpy change per mole when a

pure liquid at 1 bar vaporizes to a gas at 1 bar, as in

H2O (l) H2O (g) (373 K) = +40.66 kJmol-1

b) Standard enthalpy of transition, - the standard enthalpy change that

accompanies a change of physical state

Tb = normal boiling point of T

Tf = melting point
Fusion : entropy when melting a substance

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 c) Standard enthalpy of fusion, - enthalpy change accompanying the conversion
of a solid to liquid as in:

H2O (s) H2O (l) (273 K) = +6.01 kJmol-1

d) Standard reaction enthalpy, - the change in enthalpy when reactants in their

standard states change to products in their standard states, as in:

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) = -890 kJmol-1

______________________________________________________________________

At constant pressure, H = qrev= qp

The entropy of melting or fusion is:

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 = , Tfus = melting point

fusH = Hliquid - Hsolid

The entropy of vaporization is:

The entropy of transition is:

_____________________________________________________________________

Compressed the gas: work done on the system, w = +ve, V = -ve, V1> V2

Expanded the gas: work done by the system, w = -ve, V = +ve, V1< V2

Reversible work done on the system is (compressed the gas):

= = = -PV

The diagram below shows the expansion of gas, in which the pressure is falling as the
volume increases. The reversible work done by the system (expanded the gas):

or or wrev = -PV
is represented by the shaded area in Figure 2.4a

Irreversible expansion by dropping the external pressure to the final pressure, P2

- The irreversible work done by the system is: or

- The work done by the system is represented by the shaded area in Figure
2.4b and work is less than the reversible work

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 (a) illustrate the reversible work of expansion
from V1 to V2

(b) shows the irreversible work that would be

performed by the system if the external
pressure were suddenly dropped to the final
volume

Reversible and Irreversible Processes

In a reversible process the system is at equilibrium at every stage of the process.

An irreversible process is one where these conditions are not fulfilled.

If pint>pext in an expansion process then the process is irreversible because the

system does not remain at equilibrium at every stage of the process. For irreversible
processes, pV work must be calculated using

dw = pextdV

On the other hand, if pint = pext then the process can be carried out reversibly. Also, there
is then no need to distinguish between external pressure and internal pressure so that

pint = pext = p

dw = pdV,

and

______________________________________________________________________________

Cp - Cv = nR

or

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 Cp,m - Cv,m = R

Or

Cp,m = Cv,m +R

Or

Cv,m= Cp,m R

____________________________________________________________________

Exercise:

1) Calculate the standard Gibbs energy (G ) (in unit kJmol-1) for the combustion of methane,
CH4 at 25 C using the following data. Is the reaction spontaneous at 25 C?

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l)

Compound
H
H2O (g) 241.82 188.83
H2O (l) -285.83 69.91
H2O (s) 0 37.99
O2 (g) 0 205.0
CO2 (aq) -413.8 117.6
CO2 (g) -383.51 213.7
CH4 (g) -74.87 186.1

rG = rH -TrS

H = U + PV

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 H = U + PV PV = nRT

H = U + (nRT)

H = U + nRT

w = -PexV PexV = nRT

w = -nRT

State and Path Function

State function

- is a function depends only on the present state of a system and not on its past
history, for example depends on initial and final states.

- property of a system that depends only on the current state of the system, not
on the way in which the system acquired that state.

- State functions do not depend on the path taken at all.

Path function

- depends on the path by which the process is performed rather than on the
initial and final states.

- Path functions are functions that depend on the path taken to reach that
specific value.

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Example: The state functions in the form of enthalpy:

Precipitation of NaCI from Na+ ion and Cl- ion: Na+ + (aq) + Cl- (aq) NaCl (s)

In this figure, two different steps are shown to form NaCl(s).

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 The first path takes only one step: Na+(g) + Cl-(g) = NaCl(s), which has an enthalpy of
formation of -411 kJ/mol.

The second path takes 5 steps to form NaCl(s) and when we add the enthalpy of
formation of all these steps, the enthalpy of formation of NaCl(s) still ends up as -411
kJ/mol.

This is the epitome of state functions as we have just stated that no matter what path we
take to form NaCl(s), it still end up with the same enthalpy of formation of -411 kJ/mol.

Determination of Enthalpies of Chemical Reactions

Method 1: The Direct Method

H
Method 2: Hesss Law

Hesss Law states that the standard enthalpy of an overall reaction is the sum of the standard
enthalpies of the individual reactions into which a reaction may be divided.

Example 1:

The standard reaction enthalpy for the hydrogenation of propene is -124 kJ mol-1.

CH2=CHCH3 (g) + H2(g) CH3CH2CH3 (g)

The standard reaction enthalpy for the combustion of propane is -2220kJ mol-1.

CH3CH2CH3 (g) + 5O2 (g) 3CO2 (g) + 4H2O (l)

H2O (l) H2 (g) + 1/2O2 (g) rH = +286 kJ mol-1

Calculate the standard enthalpy and predict the sign value of entropy for combustion of
propene.

Answer:

Combustion of propene:

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C3H6 (g) + 9/2O2 (g) 3CO2 (g) + 3H2O (g)

The system becoming more disordered when the number of molecule increased. So, the
entropy increases in the system.

rH/(kJ mol-1)

C3H6 (g)+ H2 (g) CH3CH2CH3 (g) -124

C3H8 (g)+5O2 (g) 3CO2 (g) + 4H2O (l) -2220

H2O (l) H2 (g) + 1/2O2 (g) +286

C3H6 (g) + 9/2O2(g) 3CO2 (g) + 3H2O (l) -2058kJ mol-1

83
84
Example:

A sample of 5.0 mol CO2 is originally confined in 15 L at 280.5 K and then undergoes adiabatic
expansion against a constant pressure at 78.5 kPa until the initial volume increases twice.
Given that, the molar heat capacity at constant pressure (Cp,m) of CO2 is 37.11 J K-1 mol-1.
Calculate:

i) Heat (q) (in unit J)

ii) Work (w) (in unit J) (1 atm dm3 = 101.325 J)

iii) Change of internal energy (U) (in unit J)

iv) Change of temperature (T) (in unit K)

v) Change of enthalpy (H)(in unit J)

Answer:

n = 5.0 mol

Vi = 15 L

Vf = 15 L x 2 = 30 L

Ti = 280.5 K

Pext = 78.5 kPa

Cp,m= 37.11 J K-1 mol-1

i) q = 0, adiabatic

ii) w = -PextV
1 atm = 101.325 kPa

78.5 kPa x = 0.775 atm

w = - 0.775 atm x (30 15) dm3

w = - 11.625 atm dm3

1 atm dm3 = 101.325 J

w = -11.625 atm dm3 x

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 w = - 1177.9 J

iii) U= q + w

U= - 1177.9 J

iv) T?

w = n x Cv,mx T

T=

Cv,m= Cp,mR

= 37.11 J K-1 mol-1 8.314 J K-1 mol-1

= 28.796 J K-1 mol-1

T=

T = - 8.18 K

v) H = U + PV

= U + nRT

= - 1177.5 J + (5.00 mol x 8.314 J K-1 mol-1 x -8.18 K)

= - 1517.4685 J

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One mole of an ideal gas for which P = 1.00 bar and T = 300 K is expanded adiabatically
against an external pressure of 0.100 bar until the final pressure is 0.120 bar. Given that, the
molar heat capacity at constant volume (Cv,m) is 3/2 R J K-1 mol-1.

Pi = 1.00 bar

Ti = 300 K

Pext = 0.100 bar

Pf = 0.120 bar

i) Express the final temperature (Tf) for the adiabatic expansion process against the external
pressure

Because the process is adiabatic, q = 0

and
U(adiabatic) = w (expansion against a constant pressure),

Therefore

U = n Cv,m (Tf Ti) = - Pext (Vf Vi)

Using the ideal gas law

n Cv,m (Tf Ti) = - Pext + Pext

nCv,mTf nCv,mTi= - Pext +Pext

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nCv,mTf + Pext = Pext + nCv,mTi

Tf = Ti

Tf =Ti

Tf =Ti

i) Calculate the final temperature (Tf) (in unit K).

Tf =Ti

Tf = 300 K x
Tf = 205.71 K

ii) Give the value of heat (q) (in unit J).

q=0

iii) Calculate the value of work done (w) (in unit J).

U = q + w
q=0
U = w
U = w = nCv,m(Tf Ti)

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 = 1mol 12.47 J K-1 mol-1 (205.71 K 300 K)
w = - 1175.80 J

iv) Find the value for the change of internal energy (U) (in unit J).

U = w = - 1175.80 J

v) Calculate the change of enthalpy (H) (in unit kJ).

H = U + (PV)

H = U + nRT

= - 1175.80 J + [1 mol x 8.314 J K-1 mol-1 x (205.71 K 300 K)]

= - 1959.73 J = -1.9597 kJ

89