Thermodynamics Universe

References: Physical Chemistry – P. W.

System boundary Surroundings
Atkins
Have you ever wondered why things happen
in this world?
We make our observations of the system
Why does water evaporate at 100 ºC and 1
from the surroundings.
atm? Why do hot objects cool? How do we
stay alive? boundary
A part of the answer is related to energy. System
How is energy involved in making things
happen? surroundings
We need energy to move, to think and to
live. Every chemical reaction and every The system and the surroundings may be in
metabolic process make use of energy. contact and separated by a boundary (real or
These processes involve breaking bonds, imaginary). In thermodynamics we study
making bonds and rearrange bonds between the energy transformations that occur within
atoms and hence make use of energy. a system and energy transfers that occur
Thermodynamics is a branch of Chemistry between the system and the surroundings.
where we learn the science of transformation This transfer of energy can be occurred
of energy that accompanies chemical and through the boundary. There are two types
physical changes. Energy is a macroscopic of boundaries.
property (bulk property) and directly Adiabatic boundary
measurable. Thermochemistry is one branch The boundaries that do not permit energy
of thermodynamics where we study heat transfer as heat.
released or absorbed in chemical reactions. Diathermic boundary
Equilibrium and Electrochemistry are also The boundaries that do permit energy
branches of Thermodynamics. transfer as heat.
Thermodynamics helps us to understand all In thermodynamics we study three types of
processes not only in a laboratory but also in systems.
our day to day life. Thermodynamic
definition of energy is “the capacity to do
work or supply heat”. In Thermodynamics Open System
the world is devided into 2 parts. The part Closed System
System
Both matter
of the universe that undergoes a Only energy can be
and Energy can
chemical/physical change is called a system. exchanged
be exchanged
Thermodynamic system is the part of the
world that we want to study. Everything
else outside the thermodynamic system is
called surroundings. We normally consider
only the immediate surroundings of the Closed System Isolated System
thermodynamic system which can be Energy can be Neither matter nor
considered as a thermal reservoir or constant exchanged. energy is transferred
temperature water bath. Eg. Reaction vessel Matter cannot between system and
be exchanged surroundings

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Energy
Energy is the motive power of all
chemical reactions. Without energy
nothing could happen in the world.
Energy is stored in all the substances
in this world. The total energy of a
system is called the Internal
Energy, U, of a system. It is the
sum of the kinetic energies of all the
particles and all possible kinds of
potential energies. However, a
chemical/physical process can
change this internal energy. There
are three ways of increasing energy
of a system.
(1) By adding material to the
system. (2) By heating the
system.
(3) By doing work on the system.
At this level we consider energy
transformations only in closed
systems. Therefore the latter two are
the only ways of increasing energy
of a closed system.
Work (w) and Heat (q) are the two
modes of energy transfer.
Final state
∆U work
heat
Initial state
In that respect, the system can be
considered as a bank of energy. Internal
energy is stored in the bank as heat or
work. You can make transactions in two
currencies: by doing work or by heating.
You can withdraw or deposit either
currency.
The SI units of work and heat are joule
(J).
2
Heat
q>0 q<0
system
w>0 w <0
Work
Thermodynamic State of a System
Thermodynamic state is defined to describe
a thermodynamic system.
Ideal Gas
For a given amount of ideal gas, if 2 of the
three variables, P, V and T are known that
state is completely specified.
P, V and T are called state variables.
Pure substance
For a given amount of a pure substance in a
system, if any 2 of the three variables P, V
and T are known the state is completely
specified.
For any system these 3 state variables are
not independent but related by a general
formula, equation of state.
Mixture
In a mixture of C number of components,
the state is completely specified if (C-1)
composition variables are known in addition
to the 2 of the three state variables, P, V and
T.
By changing only a single variable,
thermodynamic state of a system can be
changed.
The state of a system can be changed by
performing chemical/physical processes on
the system.
state I state II
P1, V1 P2, V2
The internal energy of a system depends
only on the current state of the system. It is
independent of the path chosen to change
 the state. Therefore internal energy, U is A process which occurs without
called a state function. Thermodynamic changing the volume of the system.
properties are characterised by state Adiabatic Process
properties. Internal energy, U, is a A process which occurs without
thermodynamic property. transfer of heat between system and
The change in internal energy, ∆ U is surroundings.
independent of the path. Reversible Process
∆ U = UII – UI where, UI and UII are the A process which can be reversed at
values of internal energy of the system in the any moment by infinitesimal change
initial state (before change of state) and final of any variable. Infinitesimal change
state (after the change of state) respectively. can reverse the process to restore
both system and surroundings to
II their initial states. In this case the
∆U = ∫ dU = U 2 − U 1 system is infinitesimally close to
I equilibrium.
Irreversible Process
Heat, q, and work, w, are not state A process that cannot be reversed by
properties. They depend on the path. an infinitesimal change of a variable.
Therefore they are called path functions. All natural processes are irreversible.
They are not thermodynamic properties. Cyclic Process
They are modes of energy transfer. A process which goes through
several steps and comes back to the
II
initial state.
∫ dq = q
I
(not q II − q I ) During a cyclic process, the overall
II
change in a thermodynamic property
is zero.
∫ dw = w
I
(not w II − w I )
First Law of Thermodynamics
Thermodynamic properties can be either Suppose we have a system in a state I
extensive property or intensive property. having internal energy U1. If no external
Intensive Property forces are acting on the system, the state and
Properties whose values do not depend on hence the internal energy of the system
the mass (size) of the system remains constant. If wad amount of work is
eg. temperature, pressure, density done on the system adiabatically, without
Extensive Property any heat, state changes. The internal energy
Properties whose values depend on the mass of the new state is U2 = U1 + wad
(size) of the system. U2 –U1 = ∆ U = wad
eg. volume, internal energy As U is a state function, wad depends only on
Different Types of Processes the states but not on the path in which the
1. Isothermal Process transformation of state is performed.
A process which occurs at constant When a system undergoes an adiabatic
temperature. change, the amount of work done is
2. Isobaric Process independent of the manner in which the
A process which occurs under change is carried out, but depends only on
constant pressure. the initial and final states.
3. Isochoric Process For non-adiabatic change of state,

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∆ U≠ w
The difference ∆ U – w is called the heat
input to the system. ∆ U – w = q
∆ U=q+w
This is the mathematical expression of the
First law of thermodynamics.
∆ U – internal energy change in the system,
q – heat absorbed by the system, w – work
done on the system
For infinitesimal changes, dU = dq + dw
dU – infinitesimal change in internal energy
of the system, dq – infinitesimal amount of
heat absorbed by the system, dw –
infinitesimal amount of work done on the
system
Using the First Law of Thermodynamics we
can determine only a change in internal
energy of the system and not the absolute
value of internal energy of the system.
In an isolated system, there is no any kind of
energy transfer (neither heat nor work)
between system and surroundings and
hence, the internal energy of the system is
constant.
q = 0 and w = 0 then ∆ U = 0.
The First Law of Thermodynamics can be
expressed in a number of ways.
1. Internal energy of an isolated
system is constant.
2. Energy cannot be created or
destroyed, only can be
transformed from one form to the
other form.
3. The internal energy of a system
is constant unless it is changed
by doing work or by heating.
Work
Work in thermodynamics is defined as in
classical mechanics. When the surroundings
exerts a measurable force Fx on a system and
the system moves a distance dx at the point
of application of Fx, then the surrounding
has done work, dw = Fxdx on the system.
Fx can be mechanical, electrical or magnetic
or any kind of force.
4
When Fx and dx are in the same direction,
positive work is done on the system, dw > 0.
When Fx and dx are in opposite directions,
dw < 0.
Work for compression/expansion of a
gas (PV- Work)
Pex system(gas)
Fx → l
x b
The system consists of a gas contained
within the piston and cylinder walls. The
piston is massless, frictionless, rigid,
perfectly fitting and of cross-sectional area
A.
Let the external pressure is Pex and x denotes
the piston’s location. If Pex is now increased
by an infinitesimal amount, piston will move
inward by infinitesimal distance, dx. Thus
the volume of the gas decreases and internal
pressure will increase until it balances Pex.
The surroundings exerted a force Fx on the
system and the piston moves a distance dx.
The work done by the surroundings = Fxdx =
PexAdx
I = b-x where, b is the length of the cylinder
and x is the piston’s position.
Volume of gas in the cylinder V = Al = A(b-
x)
dV = -Adx
∴ dw = -PexdV
Work done on the system (gas) = -PexdV
For compression, dV < 0 and dw > 0 . The
work is done on the system.
For expansion, dV > 0 and dw < 0. The
work is done by the system.
Whenever there is an
expansion/compression of a gas, work done
on the system = -PexdV
From the First Law,
dU = dq – PexdV + dwother
 If only PV-work is involved in the process,
dU = dq - PexdV V1 V2 V
During chemical reactions gases are
produced and hence the volume of the 2. Free Expansion
system can be changed. Free expansion is an expansion
against vacuum. Pex = 0 and dw = 0
Application of dw = -PexdV to various There is no work done on the system
processes during free expansion.
1. Reversible isothermal 3. Expansion of gas against constant Pex
expansion/compression of ideal gas This is an irreversible process which
Let’s consider n mol of ideal gas in the occurs under constant Pex. The
initial state of (P1, V1) expands reversibly pressure of the gas is dropped
and isothermally to a final state of (P2, V2) at instantaneously from the initial
temperature T. In this process Pin and Pex pressure of P1 to the final pressure,
change gradually. Let’s assume that only P2, and then expands from V1 to V2
PV-work is involved. against constant external pressure
Pin ≈ Pex (say P ) equivalent to the final pressure of the
P is the pressure of the ideal gas. gas.
dw = -PexdV = -PdV Work done on the system, w, is
V2
Using ideal gas equation, PV = nRT
w = ∫ dw = − ∫ Pex dV
dw = -nRTdV/V
V1

w = -Pex(V2 – V1)
− nRT
w = ∫ dw = ∫ dV
V Heat
where, n is the amount of gas in the The amount of heat absorbed by a
system, T is the temperature and R the gas system depends on the conditions
constant. that we use. When two bodies of
As the process is isothermal T is different temperatures are placed in
constant. contact, they eventually reach
V2
thermal equilibrium at a particular
dV temperature.
w = − nRT ∫
V1
V If we supply dq amount of heat to a
system, its temperature rises by dT.
w = -nRTln(V2/V1)
As temperature is constant P1V1 = P2V2 dT ∝ dq
w = -nRTln(P1/P2) dq
C=
dT
PV-work is equal to the area under C – heat capacity of the system, dq –
the curve on the P-V plane. amount of heat absorbed by the
system
dT – temperature change in the
P system
Heat capacity is the measure of the
PV-isotherm capability of a system to take in
energy as heat. In other words, heat
capacity is the heat required to raise

5
the temperature of the system by 1 measuring the amount of heat
K. More heat is necessary to raise absorbed by the system under
the temperature of a large body than constant volume, ∆ U can be
a small body by 1 K. Therefore, heat determined.
capacity, C, is an extensive property. Enthalpy, H
C Chemists are much more interested
cm =
n in processes taking place at constant
cm – molar heat capacity and n – pressure. Whenever a reaction takes
amount present in the system place in a container open to the
Heat capacity depends on the atmosphere, its pressure is constant
conditions that we use. Normally, it and equal to the atmospheric
is measured under constant pressure pressure. It is convenient to define a
and volume. thermodynamic state function that
has the following property at
 ∂q  constant pressure.
at constant volume C v =  
 ∂T  v ∆ Xp=qp analogues to ∆ Uv=qv
From the First Law of
 ∂q  Thermodynamics,
at constant pressure C p =  
 ∂T  p dq = dU + PdV , if only PV-work is
Cv – isochoric heat capacity and Cp – involved.
isobaric heat capacity Adding and subtracting VdP,
dqv = CvdT or dqv = ncv.mdT dq = dU + PdV + VdP – VdP
dqp = CpdT or dqp = ncp.mdT dq = dU + d(PV) – VdP
SI units of heat capacity is J K-1 and dq = d(U + PV) – VdP
molar heat capacity is J mol-1 K-1. The function U + PV has the desired
From the First law if there is only property under constant pressure.
PV-work involved, dqp = d(U + PV)p
dU = dq - PexdV This function is called Enthalpy, H.
For isochoric heating process, dUv = H = U + PV
dqv , dUv = CvdT , dHp = dqp , ∆ Hp = qp
 ∂U  By measuring qp, ∆ Hp can be
Cv =   determined.
 ∂T  v
U, P and V are state functions.
T2 T2 Hence H is a state function. It is a
∆U v = ∫ dU v = ∫ C v dT = ∫ ncv ,m dT Thermodynamic property. H is an
T1 T1 extensive property.
In general, U = f(T, V) H = nh where h – molar enthalpy
 ∂U   ∂U  and n – amount of substance present
dU =   dT +   dV in the system
 ∂T v  ∂V T
A change in the Enthalpy of a system
For an ideal gas, U = f(T).
is equal to the heat released or
Therefore, dU = CvdT is always
absorbed at constant pressure. In
valid for ideal gas.
other words, H is a measure of the
In order to determine ∆ U for any energy of a system that can be
system, we have to do the change in released as heat. The name Enthalpy
the state under constant volume. By

6
comes from the Greek words “Heat  ∂H   ∂H 
dH =   dT +   dP
Inside”.  ∂T  p  ∂P T
For exothermic reaction, heat is Relationship between Cp and Cv
released to the surroundings. Then, for ideal gas
Enthalpy of the system decreases. H = U + PV , H = U + nRT
For endothermic reaction, heat is When the temperature is increased
absorbed by the system and hence by dT, H is increased by dH and U is
Enthalpy increases. increased by dU.
dH = dU + nRdT
Endothermic , ∆ H > 0 CpdT = CvdT + nRdT
Cp – Cv = nR
Enthalpy For 1 mol, Cm,p – Cm,v = R
Heat Enthalpy Some Applications of the First
Law of Thermodynamics

Exothermic, ∆ H < 0 1. Reversible isobaric heating of a

system
qp = ∆ Hp = ∫ nCp,mdT
Heat w = -PexdV = -P(V2 – V1)
Enthalpy ∆ U = q + w = ∫ nCp,mdT –P(V2 – V1)
Enthalpy

Change in Enthalpy ∆ H = Hfinal 2. Reversible isochoric heating of a

-Hinitial system
For endorthermic reaction at constant qv = ∆ Uv = ∫ nCv,mdT
pressure, ∆ H > 0 w = -PexdV = 0
For exothermic reactions at constant ∆ H = ∆ U + ∆ (PV) = ∆ U + P∆ V
pressure, ∆ H < 0 + V∆ P
dHp = dqp = nCm,pdT ∆ H = ∆ U + V∆ P
∆ Hp = ∫ dHp = ∫ nCm,pdT 3. Reversible isobaric heating of ideal
If Cm,p is independent of T, gas
∆ Hp = nCm,p(T2 – T1) qp = ∆ Hp = ∫ nCp,mdT
∆ U = ∫ nCv,mdT
w = -PexdV = -P(V2 – V1)
 ∂U   ∂H  4. Reversible isochoric heating of ideal
Cv =   Cp =  
 ∂T  v  ∂T  p gas
For ideal gas, internal energy is a qv = ∆ Uv = ∫ nCv,mdT
function of only temperature, U = w=0
f(T). Therefore, Enthalpy is also a ∆ H = ∫ nCp,mdT
function of only temperature, H = 5. Phase Transition
f(T). A phase change is a process in which
dHp = nCm,pdT is always valid. at least one phase appears in a
In general H = f(P,T) system without the occurence of a

7
chemical change. Phase transitions
are reversible processes which occur
at constant temperature and pressure.
eg. melting of ice, vapourization of
water, sublimation of I2
qp = ∆ Hp = Enthalpy of phase
transition
w = -P∆ V
∆ V – volume change during the
phase transition. This can be
calculated from the densities of the
two phase. If one phase is a gas we
can assume ideal behaviour for gas
and use PV = nRT to calculate the
volume in the gas phase.
∆ U = ∆ Hp - P∆ V
Thermochemistry
Thermochemistry is the study of heat
absorbed or evolved during a
chemical reaction. This is a special
application of the First Law of
Thermodynamics to study chemical
reactions. This has a great practical
importance. If q > 0 , heat is
supplied to the system and the
reaction is endothermic.
If q < 0 , heat is evolved from the
system and the reaction is
exothermic. All combustion
reactions liberate heat and
exothermic. Heat of a reaction, q,
becomes a state function under
constant pressure and volume.
Standard States
Pure solid/liquid:
The standard state is defined as its
pure form at a pressure of 1 bar at
temperature T. T is the temperature
of interest.
1 atm = 1.01325x105 Pa
1 bar = 105 Pa = 0.986923 atm
There is a single standard state for a
pure solid/liquid at each temperature.
8
eg. The standard state of liquid
ethanol at 298 K is the pure liquid at
298 K and 1 bar pressure.
Pure gas:
The standard state of a pure gas at
temperature T is the state where
pressure is 1 bar and the gas behaves
as ideal gas. Since real gases do not
behave ideally at 1 bar pressure, the
standard state of a pure gas is a
hypothetical state.
eg. The standard state of H2 gas at
500 K is the pure gas at 500 K and 1
bar pressure.
Elements:
The standard (reference) state of an
element at temperature T is the most
stable form of the element at T and 1
bar pressure.
Enthalpy of an element in its
standard state is zero.
eg. The standard state of the element
Nitrogen at 298 K is the gas of N2 at
298 K.
In text books standard state data are
quoted at a conventional temperature
of 298 K.
The standard enthalpy change is the
change in enthalpy when a system
undergoes a physical/chemical
change under standard conditions.
Initial and final substances must be
in their standard states.
Standard Enthalpy of
Vapourization
This is the enthalpy change when 1
mol of pure liquid at 1 bar pressure
vapourizes to a gas at 1 bar pressure.
eg. H2O(l) → H2O(g)
∆ H0(373 K) = 40.66 kJ mol-1
Standard Enthalpy of Fusion
This is the enthalpy change when 1
mol of pure solid at 1 bar pressure
melts to a pure liquid at 1 bar
pressure.
eg. H2O(s) → H2O(l) ∆ H (reverse process) = -∆ H
∆ H0(273 K) = 6.0 kJ mol-1 (forward process)
Standard Enthalpy of Formation
The standard enthalpy of formation
of a pure substance at a temperature
T is the enthalpy change for the vapour
formation of 1 mol of substance in
its standard state at T from the ∆ Hvap
corresponding separated elements forward reverse liquid
which are in their standard states at ∆ H >0 ∆ H<0
T.
eg. The standard enthalpy of ∆ Hfu
formation of benzene liquid at 298 K
refers to the reaction, solid
6C (s, graphite) + 3H2(g) → C6H6(l) ∆ Hsub ∆ Hsub = ∆ Hfus + ∆ Hvap
and is +49.0 kJ mol-1
The standard enthalpy of
formation of a substance is the Chemical Recactions
standard molar enthalpy of the Extent of reaction
substance. aA + bB → cC + dD
eg. 6C (s, graphite) + 3H2(g) → The ratio of the amount of each
C6H6(l) component reacted after time t to
∆ H0f (C6H6(l)) = h0m(C6H6)(l)) – their respective stoichiometric
3h0m(H2(g)) – 6h0m(C(s,graphite)) coefficients is constant.
3h0m(H2) = 6h0m(C) = 0 − dn a − dn B dnC dn D
= = = = dξ = constant
∆ H0f = h0m(C6H6) a b c d
dξ - extent of reaction. It has the
Standard Enthalpy of Combustion units of n (mol).
This is the enthalpy change for the dξ = dni/ν I
combustion of 1 mol of substance in ν i is the stoichiometric coefficient
O2 in the standard state.
of i th species, ν i > 0 for products
eg. C2H6(g) + (7/2)O2(g) → 2CO2(g)
and ν i< 0 for reactants.
+ 3H2O (l) ; ∆ H0(298 K) = dni is the amount of ith component
-1560.00 kJ mol-1 reacted after time t.
Standard Enthalpy of
If dξ = 0 no reaction at all
Neutralization
happened.
This is the enthalpy change
associated with the neutralization of dξ = 1 mol reaction occurs once
1 mol of an acid/base with a strong (reaction has completed one cycle).
base/acid at temperature T and 1 bar dξ = 2 mol reaction occurs twice
pressure. (reaction has completed two cycles).
Enthalpy is a state function. eg. N2(g) + 3H2(g) → 2NH3(g)
Enthalpy changes can be added / If dξ = 1 mol,
subtracted to obtain the value of an dn(H2) = (-3)(1 mol) = -3 mol 3
overall process. mol of H2 is lost.

9
 dn(N2) = (-1)(1 mol) = -1 mol 1 Hess’s Law
mol of N2 is lost. The overall reaction enthalpy is the sum
dn(NH3) = (2)(1 mol) = 2 mol 2 of reaction enthalpies for reaction steps
mol of NH3 is formed. which make up the reaction.

Standatd Enthalpy of Chemical

Reaction The relationship between ∆ Hr and
∆ Ur
Let’s consider a reaction in which H = U + PV
both reactants and products are in ∆ Hr = ∆ Ur + ∆ (PV)
their respective standard states. For reactions involving solids and
aA + bB → cC + dD liquids ∆ (PV) is very small. Therefore,
∆ Hr ≈ ∆ Ur.
Standard Enthalpy change = But ∆ (PV) for gases are considerably
(Standard total Enthalpy of all large. If gases are involved in a reaction
products) – (Standard totalEnthalpy
we have to consider ∆ (PV) during the
of all reactants)
reaction. Let’s assume that gases behave
= c mol x h0m, C + d mol x h0m,D – (a
ideally.
mol x h0m,A + b mol x h0m,B
∆ Hr = ∆ Ur + ∆ (nRT)
∆ H0 = ∑∆ nih0m,i = ∑ ν i∆ ξ h0m,i
∆ Hr = ∆ Ur + RT∆ ng
∆ ng – change in the amount of all gases
involved
 ∆H 0 
∆H r0 =   = ∑ν i hm0 ,i ∆ Hr = ∆ Ur + RT∑νi(g)
 ∆ξ 
∆ H0r = ∑ ν ih0m,i Determination of ∆ Hr and ∆ Ur
where ∆ H0r – Standard reaction A calorimeter is the device used to
Enthalpy, ν i – stoichiometric determine the amount of heat evolved or
coefficient of ith species absorbed in a chemical process. Constant
h0m,i – standard molar enthalpy of ith volume process can be carried out in the
species laboratory in an adiabatic calorimeter.
Standard Reaction Enthalpy is the
standard Enthalpy change per extent of
reaction when reactants and products are
in their standard states.
SI units of ∆ H0r are J mol-1. Note that
∆ H0r depends on how the reaction is
written.
eg. 2H2(g) + O2(g) → 2H2O(l)
∆ H0r(298 K) = -572 kJ mol-1
H2(g) + 1/2O2(g) → H2O(l)
∆ H0r(298 K) = -286 kJ mol-1
The standard reaction enthalpy can be
expressed in terms of standard enthalpies of
formation.
∆ H0r = ∑ ν i∆ H0f

1

Using this heat of combustion of solids and
liquids can be determined. A small known
quantity of the substance is placed in the
sample holder in the bomb. Bomb is filled
with excess O2. Ignite the sample and
measure the temperature rise of the water in
the jacket.
ΔUtotal = ΔUsys + ΔUsurr = 0
ΔUsys = -ΔUsurr = -Cv(T2 – T1) where Cv is
the heat capacity of the bomb calorimeter. It
can be determined by using a substance
whose heat of combustion is known or by
producing an equivalent temperature rise in
the jacket by electrical heating.
Second Law of Thermodynamics
Second Law of Thermodynamics is
concerned with spontaneous processes.
Spontaneous or natural process means a
process which occurs without the assistance
of any external force. They are irreversible.
Eg. Corrosion, melting of ice above 0 ˚C
temperature, water flows downhill, etc.
We have to find the driving force behind
natural processes. When we consider flow
of water downhill, it involves a decrease in
potential energy. When we stretch an elastic
band and release, it spontaneously contracts
1
decreasing its energy. However, in the
spontaneous process of evaporation of
alcohol in a container, heat is absorbed and
energy is increased. Therefore energy is not
the only deciding factor of spontaneity. In
this case, molecules are dispersed
everywhere in the container. There is an
increase of disorder or randomness of
molecules during evaporation. Molecules
become more free to move here and there.
Therefore we need a new concept to explain
this randomness. Entropy, S, is a measure
of randomness or disorder in a system.
Disorder is of 2 types.
1) positional disorder (distribution of
particles in space)
2) thermal disorder (distribution of
energy among particles)
A chemical system will adopt the most
probable distribution of energy or increase
the randomness.
The Second Law of Thermodynamics
states that the total entropy of a system
and its surroundings increase during all
spontaneous processes.
∆ Ssys + ∆ Ssurr ≥ 0
dSsys + dSsurr ≥ 0
Equal sign applies only to reversible
processes.
Nature acts to minimize energy and
maximize entropy of all processes.
dq
dS sys = rev where dqrev is the heat
T
absorbed by the system during a reversible
process and T is the absolute temperature
under which the heat is absorbed. S is a
state function and hence a Thermodynamic
Property. It is also an extensive property.
For a pur substance, S = ns where n is the
amount present in the system and s is the
molar Entropy. Entropy is measured in J K-
1
. Molar entropies of substances are given in
text books at the convential temperature.
q
∆S surr = surr
Tsurr
qsurr – heat transferred to surrounding
Tsurr - temperature of surrounding

∆ Ssys for isothermal reversible

expansion/compression of ideal gas
From the Rirst Law of Thermodynamics,
dU = dq + dw dw = -PdV and dU = 0
dq = pdV and dSsys = dq/T = PdV/T =
nR dV/V
V2
dV V 
∆S sys = ∫ dS sys = ∫ nR = nR ln 2  =
V V  V1 
1
F
 P1 
nR ln 
 P2 
ree Energy Functions
In order to find whether a reaction/process
occurs spontaneously we have to find
∆ Stotal. As it is troublesome it is convenient
to have a property of the system alone to
take as a criterion for spontaneity.
Therefore two new thermodynamic
functions have been introduced.
A = U – TS and G = H – TS
A is called Helmholtz Free Energy and G,
Gibbs Free Energy. These two functions
are used under different conditions.
dAT,V ≤ 0 dGT,P ≤ 0
Under constant temperature and volume
dA < 0 is the criterion for spontaneity of a
process.
Under constant temperature and pressure
dG < 0 is the criterion for spontaneity of a
process.
Equality sign is valid only for reversible
processes. A and G are very important free
energy functions and thermodynamic
properties of a system.