Fundamentals of Chemical Thermodynamics

Fundamentals of Chemical Thermodynamics
Introduction
Chemical energy stored by molecules can be released as heat during

chemical reactions when a fuel like methane, cooking gas or coal burns in
air. The chemical energy may also be used to do mechanical work when a
fuel burns in an engine. Thus, various forms of energy are interrelated
and under certain conditions, these may be transformed from one form
into another and from one place to another. The study of these energy
transformations forms the subject matter of thermodynamics.
 Arnold Sommerfeld, a German scientist, had said about

thermodynamics: "Thermodynamics is a funny subject. The first
time you go through it, you do not understand it at all. The second
time you go through it, you think you understand it, except for one
or two points. The third time you go through it, you know you don't
understand it, but by that time you are so used to the subject, it
doesn't bother you anymore...”
Therefore, thermodynamics is the science studies the relationship

between heat, temperature, work, and energy. The key concept is that heat
is a form of energy corresponding to a definite amount of mechanical
work. Thermodynamics is also defined as the science studies the changes
of thermal energy during chemical and physical processes.
Thermodynamics is an empirical science depends on various macroscopic

properties (like pressure, volume, and temperature) that deals with the
changes of the system at equilibrium in order to calculate some
unmeasurable variables such as; internal energy, free energy, enthalpy,
and entropy).
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Thermodynamics is not concerned about how and at what rate these

energy transformations are carried out, but is based on initial and final
states of a system undergoing the change. Laws of thermodynamics apply
only when a system is in equilibrium or moves from one equilibrium state
to another equilibrium state. Macroscopic properties do not change with
time for a system in equilibrium state.
Chemical thermodynamics
Chemical thermodynamics is the study of the interrelation between heat

and work with chemical reactions or with physical changes of state within
the confines of the laws of thermodynamics. Chemical thermodynamics
involves not only the laboratory measurements of various thermodynamic
properties, but also the application of mathematical methods to the study
of chemical questions and the spontaneity of processes.
Thermodynamic terms
We are interested in chemical reactions and the energy changes

accompanying them. For this, we need to know certain thermodynamic
terms. These are discussed below.
1) The system and the surrounding
A system in thermodynamics refers to that portion of matter under study.

The surroundings is the rest of the universe that can exchange matter and
energy with the system. System and the surroundings together constitute
the universe.
The universe = The system + The surroundings
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The boundary is the interface separating system from its surrounding.
For example, if we are studying the reaction between two substances A

and B kept in a beaker, the beaker containing the reaction mixture is the
system and the room where the beaker is kept is the surroundings.
2) Types of systems
The systems may be homogeneous (one phase) or heterogeneous (two or

more phases). Furthermore, thermodynamic systems are classified
according to the movements of matter and energy in or out of the system
and its surrounding.
1. Open System
In an open system, there is exchange of energy and matter between

system and surroundings. The presence of reactants in an open beaker is
an example of an open system.
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2. Closed System
In a closed system, there is no exchange of matter, but exchange of

energy is possible between system and the surroundings. The presence of
reactants in a closed vessel made of conducting material e.g., copper or
steel is an example of a closed system.
3. Isolated System
In an isolated system, there is no exchange of energy or matter between

the system and the surroundings. The presence of reactants in a thermos
flask or any other closed insulated vessel is an example of an isolated
system.
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3) Properties of the systems
A system will have some definite properties, which are relevant to the
thermodynamic study of the system and called thermodynamic properties.
These can further classified into:
(i) Extensive properties,

(ii) Intensive properties.
Extensive property of a system is a thermodynamic property, which is

dependent upon the quantity of matter in the system (e.g., volume,
energy, mass, ΔH). Extensive properties are additive. Its value for the
whole system is the sum of the values of individual parts.
Intensive property is a thermodynamic property, which is independent of

the mass of the system. These properties are not additive (e.g.,
temperature, pressure, ΔH/mol). The value for the whole system is not the
sum of the values for different parts.
4) The state of the system
The state of a thermodynamic system is described by its measurable or

macroscopic (bulk) properties. We can describe the state of a gas by
quoting its pressure (p), volume (V), temperature (T), amount (n) etc.
Variables like p, V, T are called state variables or state functions because
their values depend only on the state of the system (initial and final state)
and not on how it is reached.
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5) Thermodynamic processes
The process is the operation which makes changes in the state of the
system in any thermodynamic dimensions (T, P, V). Thermodynamic
processes are classified to:
1) Isothermal process (at constant T)

2) Isobaric process (at constant P)
3) Isochoric process (Isovolumic) (at constant V)
4) Adiabatic process (No exchange of heat/isolated systems)
5) cyclic process (the system undergo changes and returned to its
initial state)
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6) Reversible and irreversible processes
Reversible process is a very slow process and attain equilibrium. This

process could be reversed without any loss of energy between system and
surrounding. The reversible process must proceed through a series of
infinitesimal stages in which internal and external equilibrium are
maintained.
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Irreversible process is a fast and spontaneous process which cannot be

reversed by an infinitesimal change in external conditions; during the
process, the system makes finite departures from equilibrium (all natural
processes are irreversible processes).
7) Work
Work is the measure of energy transfer that occurs when an object is

moved over a distance d by an external force F.
W =F . d=P A d=P ∆ V
8) Heat and temperature
Heat is a form of energy, but temperature is a scale of kinetic energy of

the matter molecules. Temperature is used to measure how hot or cold an
object is.
Work and heat are path functions
Path functions are properties or quantities whose values depend on the

transition of a system from the initial state to the final state. The two most
common path functions are work (W) and heat (q).
Consider a gas sealed in a container with a tightly fitting yet movable

piston as seen below. We can do work on the gas by pressing the piston
downward, and we can heat up the gas by placing the container over a
flame or submerging it in a bath of boiling water. When we subject the
gas to these thermodynamics processes, the pressure and volume of the
gas can change.
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A convenient way to visualize these changes in the pressure and volume

is by using a Pressure Volume diagram or PV diagram. Each point on a
PV diagram corresponds to a different state of the gas. The pressure is
given on the vertical axis and the volume is given on the horizontal axis.
The work done during a thermodynamic process is equal to the area under
the curve as seen in the diagram below.
The reason why work is equal to the area under the curve is that,
W =F . dx=PA . dx=P ∆ V
Using the PV diagram, we are going to prove that work is path function.
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Graph a: Isochoric + Isobaric
Graph b: Isobaric + Isochoric
Graph c: Isothermal
Although the initial and final states are the same, the work done differs in
different paths.
Now, let us prove that work is path function, mathematically.
Reversible expansion (Pint ≈ Pext)
dV V2 P1
W =P∫ dV =nRT ∫ =nRT ln =nRT ln
V V1 P2
Expansion into vacuum (Pext = 0) (free expansion)
W =P∫ dV =0
Irreversible expansion against constant Pext
W =P∫ dV =P ( V 2−V 1 ) =P ∆ V
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Different equations according to different conditions result in different

magnitudes of work done regardless the initial and final states.
The zeroth law of thermodynamics
When a hot object is placed in thermal contact with a cold object, heat
flows from the warmer to the cooler object. This continues until they are
in thermal equilibrium (the heat flow stops). At this point, both bodies are
said to have the same “temperature”.
Therefore, the zeroth law of thermodynamics states, ''when two systems

have thermal equilibrium (equality of temperature) with a third system,
they in turn, have thermal equilibrium (equality of temperature) with each
other''.
This fact appears very obvious as it is based on our day-to-day

experience. Since this fact is not derivable from other laws, and since it
logically precedes the first and the second laws of thermodynamics.
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Heat capacity and specific heat
Usually, when energy is added to a system, the temperature of this system

increases.
q∝∆t
where, q is heat gained or lost and Δt is the change in temperature.
Heat capacity (C) is one of the most essential thermodynamic properties

of systems. Heat capacity, or thermal capacity, is the measurable physical
quantity that characterizes the amount of heat required to change a
substance’s temperature.
q=C ∆ t
q
C=
∆t
In the International System of Units (SI), heat capacity is expressed in the

unit of joule(s) (J) per kelvin (K). Usually, the unit of J/°C is often used.
You should note that the size of a Celsius degree and a Kelvin degree are
exactly the same, and therefore Δt is the same whether measured in
Celsius or Kelvin. CV and Cp denote the heat capacity at constant volume
and constant pressure, respectively.
Specific heat capacity (S) is defined as the amount of heat required to

raise the temperature of a certain mass (m) of a substance by one degree,
and it is a characteristic property of any substance. The amount of heat
gained or lost by an object when its temperature changes can be
calculated by the formula
q=m S ∆ t
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q
S=
m∆t
Specific heat is measured by units of J/kg K (SI units) or by J/g °C. fro
example, The specific heat of aluminum is 897 J/kg K. Therefore, it
requires 897 J to raise 1.00 kg of aluminum by 1.00 K.
Furthermore, the specific heat of any substance could be calculated using

a device called the calorimeter. A calorimeter is a device used to measure
changes in thermal energy or heat transfer. More specifically, it measures
calories. A calorie is the amount of energy required to raise one gram of
water by one degree Celsius. As such, the calorimeter measures the
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temperature change of a known amount of water. If a reaction is carried

out in the reaction vessel, or if a measured mass of heated substance is
placed in the water of the calorimeter, the change in the water
temperature allows us to calculate the change in thermal energy.
Calorimeter
When a mass of zinc at certain high temperature is placed in water

sample at lower temperature within the calorimeter, the heat lost by the
block of zinc will equal the heat gain by the water in the calorimeter. i.e.
∑ q=zero at equilibrium and the final temperature of the water and the
block of zinc will be the same when equilibrium is reached.
At equilibrium ∑ q=0
Heat gained by water + Heat lost by zinc = 0
( m S ∆ t )W + ( m S ∆ t )Zn=0
Example 1
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What is the energy (in kJ and kCal) required to heat 46 g of water from
8.5 °C to 74.6 °C? (specific heat of water is 4.184 J/g °C).
Solution
q=m S ∆ t
q=46× 4.184 × ( 74.6−8.5 )=12721.87 J
q=12.721 kJ
12.721
q= =3.04 kCal
4.18
Note: 1 Cal = 4.18 J and 1 J = 107 erg
Example 2
Calculate the specific heat of 360 g of gold if you know the heat capacity
is 85.7 J/ °C.
Solution
C=m S
85.7=360 × S
S=0.238J/g °C
Example 3
18.5 g of a metal initially at 298 K was absorbed 1170 J to raise its

temperature to 365.5 K. What is its specific heat?
Solution
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q=m S ∆ t
1170=18.5 × S × ( 365.5−298 )
S=0.937 J/g K
Example 4
12.4 g of Fe was heated to 97 °C and then put in 52 g of water at 21 °C.

The temperature finally reached 22.9 °C. Find the specific heat of Fe.
(specific heat of water is 4.184 J/g °C).
Solution
Heat gained by water + Heat lost by Fe = 0
( m S ∆ t ) w+ ( mS ∆ t ) Fe=0
( 52 × 4.184 × ( 22.9−21 ) )+ ( 12.4 × S × ( 22.9−97 ) ) =0
S Fe=0.4498 J/g °C
Example 5
What is the final temperature when 100 g of water at 100 °C is mixed

with 50 g of water at 10 °C in isolated system?
Solution
Heat gained by cold water + Heat lost by hot water = 0
( m S ∆ t ) w 1+ ( m S ∆ t ) w 2=0
( 50 × S × ( T f −10 ) ) + ( 100 × S × ( T f −100 ) )=0
T f =70 °C
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Quiz 1
1) How much heat is absorbed by 60 g of aluminum when it is heated

from 20 °C to 80 °C? (specific heat of Al is 0.897 J/g °C)
2) A 40 g of lead is heated from -25 °C to 200 °C. How much heat is
absorbed by the lead? (specific heat of Pb is 0.129 J/g °C)
3) The cooling system of an automobile motor contains 20×10 3 g of
water. What is the Δt of the water if the engine operates until
836000 J of heat have been added to the water? (specific heat of
water is 4.184 J/g °C).
4) What mass of water at 25 °C required to be in thermal equilibrium
with 185 g of Al initially at 150 °C to lower the temperature of Al
to 65 °C? (specific heat of water is 4.184 and Al is 0.897 J/g °C).
Latent heat (L)
Latent heat is the energy absorbed or released by a substance during a

change in its physical state (phase change) that occurs without changing
its temperature. The latent heat associated with melting a solid or freezing
a liquid is called the fusion (Lf); that associated with vaporizing a liquid
or a solid or condensing a vapor is called the heat of vaporization (Lvap).
Latent heat arises from the work required to overcome the forces that
hold together atoms or molecules in a material.
The latent heat (in units of J/g) is normally expressed as the amount of
heat per unit mass of the substance undergoing a phase change.
q=m L
q
L=
m
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For example, when a pot of water is kept boiling, the temperature remains
at 100 °C until the last drop evaporates, because all the heat being added
to the liquid is absorbed as latent heat of vaporization and carried away
by the escaping vapor molecules. Similarly, while ice melts, it remains at
0 °C, and the liquid water that is formed with the latent heat of fusion is
also at 0 °C. The latent heat of fusion for water at 0 °C is approximately
334 joules per gram, and the latent heat of vaporization at 100 °C is about
2230 joules per gram. Because the heat of vaporization is so large, steam
carries a great deal of thermal energy that is released when it condenses,
making water an excellent working fluid for heat engines.
Example 6
Calculate the energy required to convert 1g of ice at -30 °C to steam at

120 °C. (Specific heats of ice, water and steam are 2.03, 4.184 and 2.01
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J/g °C, respectively) and (latent heats of fusion and vaporization are 333
and 2257 J/g).
A) q ice=m Sice ∆t
B) q=m Lf
C) q W =m S W ∆ t
D) q=m Lvap
E) q vap=m Svap ∆ t
q total =q A +q B +q C +q D +q E
Internal energy
When we talk about our chemical system losing or gaining energy, we

need to introduce a quantity, which represents the total energy of the
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system. It may be chemical, electrical, mechanical or any other type of

energy you may think of, the sum of all these is the energy of the system.
In thermodynamics, we call it the internal energy of the system, U, which
may be defined as the sum of the kinetic and potential energies of the
particles that form the system. The internal energy of a system can be
understood by examining the simplest possible system: an ideal gas.
Because the particles in an ideal gas do not interact, this system has no
potential energy. The internal energy of an ideal gas is therefore the sum
of the kinetic energies of the particles in the gas.
The kinetic molecular theory assumes that the temperature of a gas is

directly proportional to the average kinetic energy of its particles, as
shown in the figure below.
The internal energy of systems that are more complex than an ideal gas
cannot be measured directly. Nevertheless, the internal energy of the
system is still proportional to its temperature. We can therefore monitor
changes in the internal energy of a system by watching what happens to
the temperature of the system. Whenever the temperature of the system
increases we can conclude that the internal energy of the system has also
increased.
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Temperature is therefore a state function. It depends only on the state of

the system at any moment in time, not the path used to get the system to
that state. Because the internal energy of the system is proportional to its
temperature, internal energy is also a state function. Any change in the
internal energy of the system is equal to the difference between its initial
and final values.
∆ U =U 2−U 1
The first law of thermodynamics
The first law of thermodynamics states that the energy of the universe is
constant. Energy can be transferred from the system to its surroundings,
or vice versa, but it cannot be created or destroyed. A more useful form of
the first law describes how energy is conserved. It says that any change in
the internal energy of a system is accompanied by
 heat passes into or out of the system,

 work is done on or by the system.
∆ U =q−W or q=∆U + W
For infinitesimal changes dU =d q−d W
Work and heat signs (signs rule)
The sign conventions for heat, work, and internal energy are summarized
in the figure below. The internal energy of a system decrease ( U < 0)
when the system either loses heat (q is released; negative sign) or work is
done on the system (compression; W has negative sign). Conversely, the
internal energy increase (ΔU > 0) when the system gains heat from its
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surroundings (q is absorbed; positive sign) or when the system does work

(expansion; W has positive sign).
Heat capacity at constant volume (CV) and constant pressure

(CP)
Consider a system which does not do work, e.g., 1 mole of an ideal gas at
constant volume. When energy is supplied to it in the form of heat, its
temperature rises. There will be an increase in internal energy, or the
energy contained within, corresponding to the heat put in.
This obviously manifests itself in a temperature rise (consequently when

this gas loses energy by doing work on the surroundings, such as by
adiabatic expansion, the temperature falls). Whatever this internal energy
is, it varies with respect to the temperature change in the system, i.e.,
dU ∝ dT
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so dU =CV dT
and CV= ( dU
dT ) V
Where, CV is a constant of proportionality. It is called ‘heat capacity at

constant volume’.
Correspondingly, we can have a term called ‘heat capacity at constant

pressure.’ When a system of say, 1 mole of ideal gas, is supplied with
energy in the form of heat dq, and the pressure is maintained constant, the
gas will expand. Still, after expansion, the temperature will be seen to
rise. If this rise is dT, then we can define heat capacity at constant
pressure CP as
dq=C P dT
so CP= ( dTdq )
P
Now this heat dq has been taken up by the system and it has resulted in
(i) Increase in the internal energy of the system (temperature has

risen).
(ii) Work done by the system (gas has expanded against external
pressure).
Thus, from First Law, we have
∆ U =dq−dW =dq−PdV
or dq=dU + PdV =d ( U + PV )
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For study of constant pressure processes, it is convenient to define a term

called ‘Enthalpy’ or ‘Heat Content’, H, equal to E + PV.
∴ C P= ( dH
dT )
P
Expansion of an ideal gas
In the above example, when the system of one mol of ideal gas expands
under constant pressure
dq=dU + PdV
or C P dT =C V dT + PdV
d ( PV )
so C P =CV + ( PdV
dT ) =C +(
V
dT )
C P =CV + ( d (RT
dT )
)
when PV =RT
∴ C P=C V + R
and C P −CV =R
Internal energy versus enthalpy
What would happen if we created a set of conditions under constant

volume which no work is done by the system on its surroundings, or vice
versa, during a chemical reaction? Under these conditions, the heat given
off or absorbed by the reaction would be equal to the change in the
internal energy of the system.
∆ U =q−W =∆ U =q−P ∆ V
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At constant V → P ∆ V =0
∴ ∆ U=qV
Therefore, at constant volume, the heat given off or absorbed by the

reaction is equal to the change in the internal energy that occurs during
the reaction.
However, if a gas is driven out of the flask during the reaction, the system
does work on its surroundings. If the reaction pulls a gas into the flask,
the surroundings do work on the system. We can still measure the amount
of heat given off or absorbed during the reaction, but it is no longer equal
to the change in the internal energy of the system, because some of the
heat has been converted into work.
∆ U =q−W
We can get around this problem by introducing the concept of enthalpy

(H), which is the sum of the internal energy of the system plus the
product of the pressure of the gas in the system times the volume of the
system. Enthalpy, H, is a state function since U, P, and V are state
functions.
H=U + PV
Hence, the change in the enthalpy of the system during a chemical

reaction is equal to the change in its internal energy plus the change in the
product of the pressure times the volume of the system.
∆ H =∆ U + ∆ ( PV )
Because the reaction is run at constant pressure, the change in the

enthalpy that occurs during the reaction is equal to the change in the
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internal energy of the system plus the product of the constant pressure
times the change in the volume of the system.
∆ H =∆ U + P ∆ V at constant P
Substituting the first law of thermodynamics into this equation gives the
following result.
∆ H =(q P −W )+ P ∆ V
∆ H =( q P−P ∆V )+ P ∆ V
Thus, the heat given off or absorbed during a chemical reaction at

constant pressure is equal to the change in the enthalpy of the system.
∴ ∆ H=q P
Isothermal-reversible expansion of an ideal gas (Pint ≈ Pext)
Since this process is isothermal, hence dT = 0
dU =0
dq−dW =0
and dq=dW
Let us consider one mole of an ideal gas contained in a cylinder with a

frictionless piston.
The pressure P of gas is balanced by atmospheric pressure and the

combined weight of the piston and the weights kept on it. If the weight on
the piston is slowly decreased such that the pressure exerted by the piston
is always infinitesimally less than the pressure of the gas, then the piston
will start moving up very slowly.
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If, simultaneously, we supply heat to the gas in the cylinder to maintain

its temperature at T then we have a case of isothermal reversible
expansion. If we can imagine that the weight on piston is made up of fine
sand and we imagine that the pressure is released by removing one sand
particle at a time then such a process will very closely represent a
reversible expansion.
Hence, the work done by the gas is
V2 V2
W =P∫ dV =RT ∫ dV
V1 V1
V2 P
W =RT ln =RT ln 1
V1 P2
Isothermal-irreversible expansion of an ideal gas (actual

expansion against Pext)
In isothermal irreversible expansion , internal pressure is much different

from external pressure . For example if internal pressure is much greater
than the external pressure , then as the expansion takes place against the
external pressure irreversibly, the work done is given by
V2
W =P∫ dV =P 2 ( V 2−V 1 )
V1
¿P2 ( RTP2 − RT
P1 )=RT (1−
P2
P1
)
Adiabatic-reversible expansion of an ideal gas
If the expansion is adiabatic dq=0
and hence, the first law takes the form dU =−dW
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and dU =C V dT =C V∫ dT=C V( T 2−T 1)
∴ ∆ U=C V ( T 2−T 1)
∴ W =C V (T 1−T 2)
The work done may be also calculated from
V2
W =P∫ dV =P 2 ( V 2−V 1 )
V1
W =P2 ( RPT2 − RP1T )=P2 T 1( PR2TT 1 − PR1TT 1 )

2 1 2 1
W =RT 1 ( TT1− PP1 )

2 2
Free expansion (into vacuum)
In a free expansion, gas is allowed to expand into a vacuum. This

happens quickly, so there is no heat transferred. No work is done, because
the gas does not displace anything. According to the First Law, this
means that
∆ U =0
W =0
q=0
Example 7
The work done when an ideal gas is compressed is 299 J and the heat
transfers from the gas is 70.3 J. Calculate the change in internal energy of
the gas.
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Solution
Work done when compression = work done on the gas
W =−299 J
Heat transfer from the gas q=−70.3 J
∆ U =q−W =−70.3−(−299 )=228.7 J
Example 8
Calculate the change in internal energy when an ideal gas absorbed

quantity of heat 30 J and the work done by expansion is 130 J.
Solution
Work done when expansion = work done by the gas
W =+130 J
Heat absorbed by the gas q=+30 J
∆ U =q−W =30−130=−100 J
Example 9
Calculate the quantity of heat of a system doing work equals to 20 J and

its internal energy is decreased by 30 J.
Solution
Work done by the system W =+20 J
Internal energy is decreased ∆ U =−30 J
q=∆U + W =−30+ 20=−10 J
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Example 10
Calculate the minimum work which must be done to compress 16 g of O 2

at 300 K from a pressure of 1 atm to a pressure of 100 atm. (O =16) (R =
8.314 J/mol.K).
Solution
Minimum work (slowly) ≡ Reversible
Isothermal reversible compression
P1
W =nRT ln
P2
Wt 16
n= = =0.5 mol
M .Wt 32
1
W =0.5 ×8.314 × 300× ln =−5744 J
100
Example 11
Two moles of an ideal gas are held by a piston under 10 atm and at 273
K. the pressure is suddenly released to 0.4 atm and the gas is allowed to
expand isothermally. Calculate W, q, ΔU and ΔH (R = 8.314 J/mol.K).
Solution
Suddenly (quickly) ≡ Irreversible
Isothermal irreversible expansion
P2
W =P2 ( V 2−V 1 )=nRT (1− )
P1
30
0.4
W =2× 8.314 ×273 × 1−( 10 )=278.7 J
q=∆U + W and ∆ U =0
q=W =278.7 J
∆ H =0
Example 12
100 g of CO at 298 K are held by a piston under 30 atm. The pressure is

suddenly released to 10 atm and the gas adiabatically expands. If C V for
CO = 20.8 J/K and the gas is assumed to be ideal, calculate: i) volume of
the gas, ii) ΔU, q, W, and ΔH (C=12, O=16) (R = 8.314 J/mol.K = 0.0821
L atm/mol.K).
Solution
Suddenly (quickly) ≡ Irreversible
Adiabatic irreversible expansion
i) PV =nRT
Wt 100
n= = =3.57 mol
M .Wt 28
30 ×V =3.57 ×0.0821 ×298
V =2.9 L
ii) ∆ U =C V (T 2−T 1 )
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P1 T 1
=
P2 T 2
30 298
=
10 T 2
T 2=99.3 K
∆ U =20.8 × ( 99.3−298 )=−4132.27 J
∆ U =−W
W =4132.27 J
q=0
∆ H =C P ( T 2−T 1 )
J
C P=C V+ R=20.8+8.314=29.114
K
∆ H =29.114 × ( 99.3−298 )=−5784 J
Example 13
A thermodynamic process is shown in the figure. In process ab, 600 J of

heat are added, and in process bd, 200 J of heat are added. Find:
i) Internal energy change in process ab

ii) Internal energy change in process abd
iii) Total heat added in process acd
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Solution
i) Internal energy change in process ab
Process ab is isochoric process W =0
Heat are added q=+600 J
∆ U =q=+600 J
ii) Internal energy change in process abd
Process bd is isobaric process
Heat are added q (bd)=+200 J
∆ U (bd)=q−W
W ( bd)=P ( V 2−V 1 )=8 ×10 4 × ( 5 ×10−3−2 ×10−3 ) =240 J
∆ U ( bd )=q−W =200−240=−40 J
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∆ U ( abd )=∆ U ( ab ) + ∆U ( bd )=600+(−40)=560 J
iii) Total heat added in process acd
q ( acd )=∆ U ( acd)+W (acd )
∆ U ( acd ) =∆ U ( abd )=560 J
W ( acd )=W ( ac ) +W (cd )
W ( cd )=0 Isochoric process
W ( ac )=P ( V 2−V 1 )=3 ×10 4 × ( 5 ×10−3 −2× 10−3 ) =90 J
q ( acd )=560+90=650 J
Quiz 2
1) An ideal gas is compressed from 0.4 L to 0.2 L under constant

external pressure of 3 atm. If the gas absorbed 13 J heat, calculate
W and ΔU.
2) 1 g of water is vaporized isobarically at 10132 N/m 2 (Pa). Its
volume in the liquid state and vapor state were 0.5 and 0.7 m3,
respectively. Find the work done by the system and the change in
internal energy. (Lvap= 2257 J/g)
3) When a system is taken from state A to state B along the path
ACB, 80 J of heat flow into the system and the system does 30 J of
work,
a) How much heat flow into the system along the path ADB if the
work done by the system is 10 J.
b) What is the quantity of heat if the system returned from the state
B to A along the curved path. The work done on the system is 20 J.
34
c) Find the heat absorbed in the path AD and DB if E(A) = 0 and

E(D) = 40 J.
The second law of thermodynamics
The first law allows us to convert heat into work, or work into heat. It
also allows us to change the internal energy of a system by transferring
either heat or work between the system and its surroundings. However, it
does not tell us whether one of these changes is easier to achieve than
another. Our experiences, however, tell us that there is a preferred
direction to many natural processes. We are not surprised when a cup of
coffee gradually loses heat to its surroundings as it cools, for example, or
when the ice in a glass of lemonade absorbs heat as it melts.
35
Nevertheless, we would be surprised if a cup of coffee suddenly grew

hotter until it boiled or the water in a glass of lemonade froze on a hot
summer day, even though neither process violates the first law of
thermodynamics.
Many chemical and physical processes are reversible and yet tend to
proceed in a direction in which they are said to be spontaneous. This
raises an obvious question: What makes a reaction or a process
spontaneous? What drives the reaction in one direction and not the other?
Spontaneous processes are the processes that proceed without any outside
assistance.
36
The gas in vessel A will spontaneously effuse into vessel B, but it will
not spontaneously return to vessel A. Spontaneous processes in one
direction are nonspontaneous in the reverse direction.
Thus, the tendency of a spontaneous reaction is governed by an important

factor. This factor, known as entropy, is a measure of the disorder of the
system. i.e. The second law of thermodynamics determines the direction
of the process. Spontaneous processes are irreversible processes.
In reversible processes, the system can be returned to its initial conditions

along the same path on the PV diagram and every point in the path is in
an equilibrium state. It is slowly process (quasi-static) and ideal process.
37
The second law of thermodynamics states the limitations on heat when it

is converted into work. The second law has been stated in two statements;
Kevin-Plank statement and Clausius statement.
Kevin-Plank statement
It is impossible to construct a device, which would operate in cycles and

produce no effect other than to extract heat from a source and convert it
completely into work. This means that it is impossible to devise a heat
engine that can absorb energy in the form of heat as well as produce work
of an equivalent amount.
Clausius statement
It is impossible for heat to move by itself from a lower temperature

reservoir to a higher temperature reservoir. That is, heat transfer can only
occur spontaneously in the direction of temperature decrease. For
example, we cannot construct a refrigerator that operates without any
work input.
38
The second law of thermodynamics describes the relationship between

entropy and the spontaneity of natural processes. i.e. In an isolated
system, natural processes are spontaneous when they lead to an increase
in disorder, or entropy. According to the second law, the total entropy of
the universe always increases. In addition, the entropy of a system either
increases or remains constant in any spontaneous process; it never
decreases. For reversible processes that reaching back to the initial
states, the change in entropy is zero. That is, the entropy of system does
not change over a complete reversible cycle.
 For any spontaneous process ∆ S univ ≥ 0
∆ S univ=∆ S sys +∆ S Surr
 In reversible processes ∆ S sys=0
 In irreversible processes ∆ S sys>0
39
Entropy
Entropy is a Greek word meaning ‘change’ and it is a measure of the

randomness of a system since increase in entropy has been seen to be
associated with increase in disorder or randomness. It is a state function.
∆ S=S 2−S 1For a process occurring at constant temperature (an isothermal
process), the change in entropy is equal to the heat that would be

transferred if the process were reversible divided by the absolute
temperature and commonly expressed in units J/K or J/mol.K,
dq
dS=
T
Example 14
Calculate the change in entropy for a cup of tea at 70 °C absorbs 100 J of

heat from its surrounding at 25 °C. Predict the process is spontaneous or
not.
Solution
40
∆ S univ=∆ S sys +∆ S surr
q 100
∆ S sys= = =0.292 J / K
T 70+273
q −100
∆ S surr= = =−0.336 J /K
T 25+273
∆ S univ=0.292+ (−0.336 )=−0.044 J / K
The process is non-spontaneous
41
Entropy change for an ideal gas (Combination of first and

second law)
dq=dU + dW
nRT
since dU =C v dT dW =PdV P=
V
dq=C v dT + PdV
dV
¿ C v dT +nRT ÷T
V
dq dT dV
=C v +nR
T T V
T2 V2
dT dV
dS=C v ∫ +nR ∫
T1 T V1 V
T2 V2 T2 P1
∴ ∆ S=C v ln +nR ln =C v ln + nR ln
T1 V1 T1 P2
Entropy change in an isothermal process
dq dW PdV
dS= = =
T T T
nRT dV
¿
V T
V2
dV
dS=nR ∫
V1 V
V2
∆ S=nR ln
V1
Entropy change during phase change
42
Consider a system and its surroundings at the transition temperature, Ttrans,

(temperature at which two phases are in equilibrium at a pressure 1 atm).
At Ttrans, any transfer of heat between the system and its surroundings is
reversible (two phases are in equilibrium).
At constant pressure, q=∆ H trans
q
since ∆ S=
T
∆ H trans
∴ ∆ S trans=
T trans
Example 15
The enthalpy change of fusion of ethanol is 4.6 kJ at its melting point 156
K. what is ΔSfusion?
Solution
∆ H fusion
∆ S fusion=
T fusion
4.6
¿ =0.0295 kJ /K
156
Entropy change in chemical reaction systems (ΔSsys)
The entropy values at 298 K and 1 atm pressure are called standard
entropies, S°. Difference in molar entropy between products and reactants
in their standard states is called the standard entropy change of the
reaction, ΔS°. Consider the general reaction
aA + bB → cC + dD
43
∆ S °=∑ S ° products−∑ S ° reactants
∆ S °= [ c S ° ( C ) +d S ° ( D ) ]−[ a S ° ( A )+ b S ° ( B ) ]
Example 16
Calculate the standard entropy change for the reaction:
2CO(g) + O2(g) → 2CO2(g)
Solution
S°(CO2)=213.6 J/K mol, S°(CO)=197.9 J/K mol, S°(O2)=205.1 J/K mol,
∆ S °= [ 2 ×213.6 ] −[ ( 2× 197.9 )+ 205.1 ]=−173.7 J / Kmol
Prediction of entropy change during chemical reaction
1) If the reaction produces more gas molecules than it consumes, ΔS

> 0.
2) If the total number of gas molecules decreases, ΔS < 0.
3) Solids are much more regular (less entropy) than liquids than
gases. (gas > liquid > solid in entropy)
4) Increasing number of molecules (moles) in the system means
increasing the amount of disorder (increasing entropy).
Quiz 3
1) Which one of the following reactions is most likely to have a

positive entropy change?
a) N2 (g) + 3H2 (g) 2 NH3 (g)
b) H2O (l) H2O (g)
44
c) CaCO3 (s) CaO (s) + CO2 (g)
d) NH4NO3 (s) + H2O (l) NH4+ (aq) + NO3¯ (aq)
e) NO (g) + O3 (g) → NO2 (g) + O2 (g)
2) Place these compounds in order of increasing S: PCl 5(s) , PCl5(g) ,

PCl3(g)
Free energy
Entropy changes, as explained, could be used to predict the spontaneity of

the thermodynamic processes in isolated systems. In addition, many
spontaneous reactions are exothermic that it is tempting to assume that
one of the driving forces that determines whether a reaction is
spontaneous is a tendency to give off energy. However, there are some
spontaneous processes accompanying with decrease in the entropy
change of the system and/or absorbing energy. Therefore, determining
one function of ΔS or ΔH does not help predicting the direction of the
process or the chemical reaction. Conveniently, both of these factors are
rolled into one convenient value called the free energy.
Free energy is the energy available in a system to do useful work. The

change in free energy during a reaction provides useful information about
the reaction's energetics and spontaneity (whether it can happen without
added energy). Free energy is expressed in two forms: the Helmholtz free
energy A, and the Gibbs free energy G. If U is the internal energy of a
system, PV the pressure-volume product, and TS the temperature-entropy
product, then A = U − TS and G = H – TS. Free energy is an extensive
45
property, meaning that its magnitude depends on the amount of a

substance in a given thermodynamic state.
Helmholtz free energy (A)
A=U−TS
For infinitesimal change dA=dU−TdS−SdT
∵ dU=dq−dw=TdS−PdV
∴ dA=TdS−PdV −TdS−SdT
dA=−PdV −SdT
∴ A is function of T & V
i.e. A = A(T,V)
dA
( )
At constant V: dT V=−S
dA
( )
At constant T: dV T=−P
 For processes occurring at constant T: ∆ A=∆ U −T ∆ S
Gibbs free energy (G)
G=H −TS
For infinitesimal change dG=dH−TdS−SdT
∵ dH=d ( U + PV )=dU + PdV +VdP
∴ dG=dU + PdV +VdP−TdS−SdT
∵ dU=dq−dw=TdS−PdV
46
∴ dG=TdS−PdV + PdV +VdP−TdS−SdT
dG=VdP−SdT
∴ G is function of T & P
i.e. G = G(T,P)
dG
( )
At constant P: dT P=−S
dA
( )
At constant T: dP T=V
 For processes occurring at constant T: ∆ G=∆ H−T ∆ S
Meaning and importance of A and G
Helmholtz free energy (A)
A=U−TS
For infinitesimal change dA=dU−TdS−SdT
∵ dU=dq−dw=TdS−dW
∴ dA=TdS−dW −TdS−SdT
At constant T ( dA ) T=−dW max
∴−( ∆ A ) T=W max
i.e. The decrease in A = The work done (maximum work) by the

system at constant temperature. The maximum work here
represents all types of work (expansion / electrical / creating
surface area / giving definite shape and volume / …).
Gibbs free energy (G)
47
G=H −TS
For infinitesimal change dG=dH−TdS−SdT
∵ dH=d ( U + PV )=dU + PdV +VdP
∴ dG=dU + PdV +VdP−TdS−SdT
At constant T& P ( dG ) T,P=dU + PdV −TdS
∵ dU=dq−dw=TdS−dW
dU −TdS=−dW
∴ ( dG ) T,P=PdV −dW max
−( dG ) T,P=dW max −PdV
∴−( ∆ G ) T.P=W useful
i.e. The decrease in A = The useful work done [all the reversible
work done except PV work (expansion work)] by the system at
constant temperature.
Reactions with a negative ∆G release energy, which means that they can
proceed without an energy input (spontaneous). In contrast, reactions
with a positive ∆G need an input of energy in order to take place (non-
spontaneous). If ∆G equals zero, the reaction is said to be at equilibrium.
Gibbs free energy and chemical reactions (Driving forces)
Some reactions are spontaneous because they give off energy in the form
of heat (∆H < 0). Others are spontaneous because they lead to an increase
48
in the disorder of the system (∆S > 0). Calculations of ∆H and ∆S can be
used to probe the driving force behind a particular reaction.
Example 17
Calculate ∆H° and ∆S° for the following reaction and decide in which
direction each of these factors will drive the reaction.
N2 (g) + 3 H2 (g) 2 NH3 (g)
∆H° (kJ/mol) 0 0 -46.11
S° (J/mol-K) 191.61 130.68 192.45
Solution
∆ H °=∑ H ° products−∑ H ° reactants
∆ H °=[ 2 ×−46.11 ] −[ ( 1× 0 ) + ( 3 ×0 ) ]
¿−92.22 k J /mol
The reaction is exothermic (∆H° < 0), which means that the enthalpy of
reaction favors the products of the reaction:
∆ S °=∑ S ° products−∑ S ° reactants
∆ S °= [ 2 ×192.45 ] − [( 1 ×191.61 ) + ( 3 ×130.68 ) ]
¿−198.75 J /mol K
The entropy of reaction is unfavorable, however, because there is a

significant increase in the order of the system, when N2 and H2 combine
to form NH3.
49
Therefore, what happens when one of the potential driving forces behind
a chemical reaction is favorable and the other is not? We can answer this
question by defining the Gibbs free energy (G) of the system, which
reflects the balance between these forces.
The Gibbs free energy of a system at any moment in time is defined as

the enthalpy of the system minus the product of the temperature times the
entropy of the system.
G=H −TS
The Gibbs free energy of the system is a state function because it is

defined in terms of thermodynamic properties that are state functions (H
and S). Thus, the change in the Gibbs free energy of the system that
occurs during a reaction is therefore equal to the change in the enthalpy
of the system minus the change in the product of the temperature times
the entropy of the system.
∆ G=∆ H−∆(TS)
If the reaction is run at constant temperature, this equation can be written

as follows.
∆ G=∆ H−T ∆ S
The change in the free energy of a system that occurs during a reaction
can be measured under any set of conditions. If the free energy is
calculated under standard conditions (pure solids, pure liquids, 1 M conc.
of solutions, 1 atm pressure of gases), the result is the standard free
energy change of the reaction (∆G°).
∆ G °=∆ H °−T ∆ S °
50
Note: the standard free energy change of an element is zero.
The change in the free energy of the system that occurs during a reaction
measures the balance between the two driving forces that determine
whether a reaction is spontaneous. As we have seen, the enthalpy and
entropy terms have different sign conventions.
Favorable Unfavorable
∆Ho < 0 ∆Ho > 0
∆S° > 0 ∆S° < 0
Because of the way the free energy of the system is defined, ∆Go is
negative for any reaction for which ∆Ho is negative and ∆So is positive.
∆Go is therefore negative for any reaction that is favored by both the
enthalpy and entropy terms. We can therefore conclude that any reaction
for which ∆Go is negative should be favorable, or spontaneous.
Favorable, or spontaneous reactions: ∆Go < 0
Conversely, ∆Go is positive for any reaction for which ∆Ho is positive and
∆So is negative. Any reaction for which ∆Go is positive is therefore
unfavorable.
Unfavorable, or non-spontaneous reactions: ∆Go > 0
Reactions are classified as either exothermic (∆H < 0) or endothermic

(∆H > 0) on the basis of whether they give off or absorb heat. Reactions
can also be classified as exergonic (∆G < 0) or endergonic (∆G > 0) on
51
the basis of whether the free energy of the system decreases or increases
during the reaction.
∆H ∆S ∆G Reactions characteristics
‫ــ‬ + Always negative Reaction is spontaneous at all T
+ ‫ــ‬ Always positive Reaction is non-spontaneous at all T
negative at low T Reaction is spontaneous at low T

‫ــ‬ ‫ــ‬
positive at high T Reaction is non-spontaneous at high T
positive at low T Reaction is non-spontaneous at low T

+ +
negative at high T Reaction is spontaneous at high T
The balance between the contributions from the enthalpy and entropy
terms to the free energy of a reaction depends on the temperature at which
the reaction is run.
Example 18
Use the values of ∆H° and ∆S° calculated in example 17 to predict

whether the following reaction is spontaneous at 25C:
N2 (g) + 3 H2 (g) 2 NH3 (g)
Solution
52
T =25+273=298 K
∆ G °=∆ H °−T ∆ S °
∆ G °=(−92.22 ×103 )−( 298 ×−198.75 )
∆ G °=−32960 J /mol=−32.96 kJ /mol
According to this calculation, the reaction should be spontaneous at 25

°C.
In addition, we define the change in Gibbs free energy for the following
chemical reaction as,
aA + bB → cC + dD
∆ G °=G ° products−G ° reactants
∆ G °=∑ ∆ G° products−∑ ∆ G ° reactants
Example 19
Determine ∆Gf° for the following combustion reaction:
CH4 (g) + 2 O2 (g) → CO2 (g) + 2 H2O (l)
∆Gf° (kJ/mol) -50.80 0 -394.36 -237.15
Note: ∆Gf° is the standard Gibbs free energy of formation (when one
mole of the compound is made from its constituent elements in their
standard states).
Solution
53
∆ G f °=∑ ∆ G f ° products−∑ ∆G f ° reactants
∆ G f °=¿
¿−817.86 kJ /mol and the reaction is spontaneous.
Gibbs free energy and chemical equilibrium
When a reaction leaves the standard state because of a change in the ratio
of the concentrations of the products to the reactants, we have to describe
the system in terms of non-standard free energies of reaction, ∆G. The
difference between ∆Go and ∆G for a reaction is important. There is only
one value of ∆Go for a reaction at a given temperature, but there are an
infinite number of possible values of ∆G.
Consider the general reversible reaction,
aA + bB cC + dD
The non-standard Gibbs free energy is,
∆ G=∆ G °+ RT lnQ
where
[C ]c [ D]d
Q=
[ A ] a [ B] b
At equilibrium: ∆ G=0 and hence, Q=K eq
so ∆ G °=−RT ln K eq
[C ] c [ D ] d
∴ ∆ G° =−RT ln
[ A] a[B] b
54
[C ] c [ D ] d
The expression , into which any values of concentrations may be
[ A] a [ B ] b
used, and which appears in many different contexts, is known as the
equilibrium quotient and is often abbreviated as Q. Only when the actual
equilibrium concentrations are substituted does Q=K eq , the equilibrium
constant.
Example 20
The standard free energy change for the reaction:
N2 (g) + 3H2 (g) → 2NH3 (g) ΔG° = -33.3 kJ
Calculate ΔG at 298 K if the reaction mixture contains 0.757 atm H 2 (g),

0.836 atm N2c(g), and 5.78 atm NH3 (g). (R = 8.314 J/mol.K)
Solution
∆ G=∆ G °+ RT lnQ
2
P ( NH 3 ) 2 ( 5.78 )
Q= = =92.1
P ( N2) P ( H2) 3 ( 0.836 ) ( 0.757 )3
∴ ∆ G=(−33.3× 103 ) +8.314 × 298 ln 92.1
¿−22094 J =−22.094 kJ
Example 21
Use the value of ΔG° obtained in example 18 to calculate the equilibrium

constant for the following reaction at 25C:
N2 (g) + 3 H2 (g) 2 NH3 (g)
55
Solution
∆ G °=−RT ln K eq
∆ G °=−RT ln K eq
−32960=−8.314 ×298 × ln K eq
ln K eq=13.3
∴ K eq=5.9× 105
Quiz 4
1) Predict whether the following reaction is still spontaneous at 500C:
N2 (g) + 3 H2 (g) 2 NH3 (g)
Use the values ∆H° and ∆S° from example 17.
2) Calculate ∆H° and ∆S° for the following reaction:
NH4NO3 (s) + H2O (l) → NH4+ (aq) + NO3¯ (aq)
Compound ∆H° (kJ/mol) ∆S° (J/mol-K)
NH4NO3(s) -365.56 151.08
NH4+ (aq) -132.51 113.4
NO3¯ (aq) -205.0 146.4
Use the results of this calculation to determine the value of ∆G° for
this reaction at 25 °C, and explain why NH4NO3 spontaneously
dissolves is water at room temperature.
56
3) Use the following standard free energy of formation data to

calculate the equilibrium constant (Ka) at 298 K for the dissociation
of formic acid: (R = 8.314 J/mol.K)
HCO2H (aq) H+ (aq) + HCO2¯ (aq)
Compound ΔGfo (kJ/mol)
HCO2H (aq) -372.3
H+ (aq) 0.00
HCO2¯ (aq) -351.0
57

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Fundamentals of Chemical Thermodynamics

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Fundamentals of Chemical Thermodynamics

Chemical energy stored by molecules can be released as heat during

 Arnold Sommerfeld, a German scientist, had said about

Therefore, thermodynamics is the science studies the relationship

Thermodynamics is an empirical science depends on various macroscopic

Thermodynamics is not concerned about how and at what rate these

Chemical thermodynamics is the study of the interrelation between heat

We are interested in chemical reactions and the energy changes

1) The system and the surrounding

A system in thermodynamics refers to that portion of matter under study.

The universe = The system + The surroundings

The boundary is the interface separating system from its surrounding.

For example, if we are studying the reaction between two substances A

The systems may be homogeneous (one phase) or heterogeneous (two or

In an open system, there is exchange of energy and matter between

In a closed system, there is no exchange of matter, but exchange of

In an isolated system, there is no exchange of energy or matter between

3) Properties of the systems

(i) Extensive properties,

Extensive property of a system is a thermodynamic property, which is

Intensive property is a thermodynamic property, which is independent of

4) The state of the system

The state of a thermodynamic system is described by its measurable or

1) Isothermal process (at constant T)

6) Reversible and irreversible processes

Reversible process is a very slow process and attain equilibrium. This

Irreversible process is a fast and spontaneous process which cannot be

Work is the measure of energy transfer that occurs when an object is

8) Heat and temperature

Heat is a form of energy, but temperature is a scale of kinetic energy of

Work and heat are path functions

Path functions are properties or quantities whose values depend on the

Consider a gas sealed in a container with a tightly fitting yet movable

A convenient way to visualize these changes in the pressure and volume

Graph a: Isochoric + Isobaric

Graph b: Isobaric + Isochoric

Now, let us prove that work is path function, mathematically.

Reversible expansion (Pint ≈ Pext)

Expansion into vacuum (Pext = 0) (free expansion)

Irreversible expansion against constant Pext

Different equations according to different conditions result in different

The zeroth law of thermodynamics

Therefore, the zeroth law of thermodynamics states, ''when two systems

This fact appears very obvious as it is based on our day-to-day

Heat capacity and specific heat

Usually, when energy is added to a system, the temperature of this system

where, q is heat gained or lost and Δt is the change in temperature.

Heat capacity (C) is one of the most essential thermodynamic properties

In the International System of Units (SI), heat capacity is expressed in the

Specific heat capacity (S) is defined as the amount of heat required to

Furthermore, the specific heat of any substance could be calculated using

temperature change of a known amount of water. If a reaction is carried

When a mass of zinc at certain high temperature is placed in water

Heat gained by water + Heat lost by zinc = 0

q=46× 4.184 × ( 74.6−8.5 )=12721.87 J

Note: 1 Cal = 4.18 J and 1 J = 107 erg

18.5 g of a metal initially at 298 K was absorbed 1170 J to raise its

12.4 g of Fe was heated to 97 °C and then put in 52 g of water at 21 °C.

Heat gained by water + Heat lost by Fe = 0