05

Thermodynamics Revision Notes

The laws of thermodynamics deal with the energy changes of macroscopic systems
involving a large number of molecules rather than microscopic systems containing a
few molecules.

Fundamentals of Thermodynamics
Some basic terms and concepts commonly used in thermodynamics are briefly
explained below:

System and Surroundings

System is a part of universe under observation and the part of the universe except
system is called surroundings. System basically a specific portion which is considered
under thermodynamic studies.
Thus, system and the surrounding together constitute the universe, i.e.
universe = system + surroundings
On the basis of exchange of mass and energy, systems are of three types:
1. Open System In which energy and matter both can be exchanged with
surroundings.
2. Closed System In which only energy can be exchanged with surroundings.
3. Isolated System In which neither matter nor energy can be exchanged with
surroundings.

Extensive and Intensive Properties

Properties used to define the state of a system are extensive and intensive properties.
1. Intensive Properties Those properties that depend on nature of matter but do not
depend on quantity of the matter, e.g. pressure, temperature, specific heat, melting
point etc.
 2. Extensive Properties Those properties that depend on
quantity of the matter present in the system, e.g. internal
Concept of Work
energy, heat, total moles, volume, enthalpy, entropy, l The work is said to be done when gas expands or
free energy etc. contracts against the external pressure. Work done is a
Force is extensive property but pressure is intensive path function not a state function as depends upon the
property. path followed.
W = - pext ´ DV
State and Path Functions For expansion W = - pext (V2 - V1 ) [Here, V2 > V1 ]
1. State Functions Those functions which depend only on For compression W = - pext (V2 - V1 ) [Here, V2 < V1 ]
the state of the system and not on how it is reached. l Maximum work done for reversible isothermal process
e.g. pressure, volume, temperature, DH, DE etc.
V
2. Path Functions The functions that depend upon the Wrev = -2.303 nRT log 2
V1
path followed are called path functions, e.g. work done,
heat etc. where, V2 = final volume, V1 = initial volume
p
Also, Wrev = -2 . 303 nRT log 1
p2
Types of Processes Maximum work done for irreversible isothermal expansion
The state of a variable can be changed by means of a (i) Intermediate expansion
thermodynamic process. These are of the following types : V2
pext < pgas, Wirr = ò pext dV
1. Adiabatic Process In which system does not exchange V1
heat with its surrounding, i.e. dQ = 0. W = - pext (V2 - V1 )
2. Isothermal Process In which temperature remains
(ii) Free expansion If gas expands in vacuum, pext = 0,
fixed, i.e. dT = 0.
therefore, W = 0
3. Isobaric Process In which change of state is brought
about at constant pressure, i.e. dp = 0. Sign Convention
4. Isochoric Process In which volume of the system (i) If W is positive — work done on the system
remains constant, i.e. dV = 0.
(ii) If W is negative — work done by the system
5. Cyclic Process This is the process in which a system
undergoes a number of different states and finally
returns to its initial state. For such a process, change in Heat
internal energy and enthalpy is zero, i.e. dE = 0 and
It is defined as the quantity of energy, which flows between
dH = 0.
system and surroundings on account of temperature difference.
6. Reversible Process In this process, (quasistatic system), It is also a path function, i.e. depends upon the path followed.
change taken place is infinitesimally slow and their
direction at any point can be reversed by infinitesimal
change in the state of the system. Reversible process is
Sign Convention
an ideal process and here, every intermediate state is in
equilibrium with others, if any. (i) If q is positive — heat is supplied to the system
7. Irreversible Process This process, is the one which (ii) If q is negative — heat is lost by the system
cannot be reversed. In this process, amount of energy
increases. All natural processes are irreversible in Internal Energy (E or U)
nature.
l It is the total energy within the substance. It is equal to the
• If macroscopic properties like temperature, pressure, etc., sum of translational energy, vibrational energy, potential
NOTE do not change with the time, the system is said to be in energy etc. We can only determine the change in internal
thermodynamic equilibrium. energy.
• If the two systems are in thermal equilibrium with a
third system, they must be in thermal equilibrium i.e. DU = U2 - U1
with each other. This law is known as zeroth law of l At constant temperature, internal energy change (DE) will
thermodynamics. be zero. Internal energy depends on temperature,
The law defines the temperature as the property pressure, volume and quantity of matter.
which determines, whether the body is in thermal
equilibrium or not.
 There are two types of heat capacities based on the conditions
First Law of Thermodynamics such as volume and pressure.
According to this law, energy can neither be created nor 1. Heat Capacity at Constant Pressure (C p) The heat
destroyed although it may be converted from one form to
capacity of a substance measured when the gaseous
another.
system is at constant pressure.
l Mathematical form of first law of thermodynamics,
æ q ö dH
DE =q +W Cp = ç ÷ or C p =
è DT ø p dT
l Both W and q are not state functions but quantity W + q is
a state function. 2. Heat Capacity at Constant Volume (CV ) The heat
capacity of a substance measured when the gaseous
system is at constant volume.
Enthalpy
æ q ö dV
l The total heat content of a system at constant pressure is CV = ç ÷ or CV =
è DT ø V dT
called the enthalpy of the system. It is the sum of internal
energy and the product of pressure-volume work. l Relationship between C p and CV is given as
l It is an extensive quantity, state function and C p - CV = R (R is the molar gas constant.)
represented by the symbol H. R
C p - CV =
The equation is M
H = E + pV
l For monoatomic gas the molar heat capacity at
æ3ö
DH = DE + pDV constant volume, CV = ç ÷ R
è2ø
DH = DE + Dng RT l For monoatomic gas molar heat capacity at constant
where, DH = enthalpy change pressure,
Dng = gaseous moles of products - gaseous æ3ö æ5ö
Cp = ç ÷ R + R = ç ÷ R
moles of reactants è2ø è2ø
l If Dng = 0, then DH = DU; If Dng > 0 then DH > DU and Cp æ 5 ö
l Poisson’s ratio, g = = ç ÷ = 1.66
if Dng < 0 then, DH < DU. CV è 3 ø
l For reaction involving solids and liquids only, DH = DE . g = 1.66 for monoatomic gases (like He, Ar)
Enthalpy also changes, when a substance undergoes
g = 1.40 for diatomic gases (like H2 , O2 , CO)
phase transition.
g = 1.33 for triatomic gases (like H2O, O3 )
Work done in reversible adiabatic expansion
Heat Capacity l

Work done = CV DT = CV ´ (T2 - T1 )

Heat capacity (C) of a system is defined as the amount of heat
required to raise the temperature of the system by 1 ° C. NOTE The molar heat capacity for any process is given by
q R
C= C = CV +
DT 1 -g
when, pV g = constant
l If the system consists of a single substance or a solution
and weighs 1 mol, the heat capacity of the system is
referred as molar heat capacity (Cm).
Kirchhoff’s Equation
According to Kirchhoff’s equation, the partial derivatives of
l If the system consists of a single substance or a solution the change of enthalpy (or of internal energy) during a
and weights 1 g, the heat capacity of the system is reaction, with respect to temperature at constant pressure
referred as specific heat of the system (Cs ). (or volume) equals to the change in heat capacity at constant
pressure (or volume).
q = C ´ m ´ DT
where, m = mass of substance, DH2 - DH1 DE2 - DE1
DC p = and DCV =
T2 - T1 T2 - T1
C = specific heat capacity
where, DC p = SC p of products - SC p of reactants
and DT = temperature difference.
DCV = SCV of products - SCV of reactants
 This is the mathematical statement of the second law of
Entropy Change (DS ) thermodynamics.
Entropy is the measurement of randomness or disorder of the
molecules. A process which proceeds at its own without any Carnot Engine
outside help is termed as spontaneous process. The total
entropy change (DS total ) for the system and surrounding of a Carnot in 1824 gave an imaginary reversible cycle which
spontaneous process is always positive, demonstrates the maximum conversion of heat into work. He
actually proposed a theoretical heat engine to show that its
DS total = DSsystem + DSsurrounding > 0. efficiency was based upon the temperatures, between which
l Entropy is a state function and depends only on initial it operated.
and final states of the system. A Carnot cycle comprises four operations or processes:
i.e. DS = S final - S initial (i) Isothermal reversible expansion
l Unit of entropy is joule per Kelvin per mole. (ii) Adiabatic reversible expansion
l For a reversible change at constant temperature (iii) Isothermal reversible compression
q (iv) Adiabatic reversible compression
DS = rev = S final - S initial
T
q rev = heat absorbed or evolved at absolute temperature T. A(p1,V1) Isothermal
If DS > 0, heat is absorbed and if DS < 0, heat is evolved. expansion
B(p2,V2)
l For a spontaneous isothermal expansion
V Adiabatic
DS = 2.303 nR log 2 Pressure compression Adiabatic
V1 expansion
D(p4,V4)
l The change of matter from one state to another is called C (p3,V3)
phase transition. Isothermal
compression
The entropy changes at the time of phase transition are as Volume
follows:
Carnot cycle
DH fusion
(i) DS melting = ; (Tm = melting point of
Tm l Net work done in 1 cycle is
substance) V2 V
W = RT2 ln + RT1 ln 4
DH vaporisation V1 V3
(ii) DS vaporisation = ; (Tb = boiling point of
Tb l Net heat absorbed in the whole cycle is
substance) V
q = R (T2 - T1 ) ln 2
DHsublimation V1
(iii) DSsublimation = ; (Tsub = sublimation
Tsub l Efficiency of a heat engine (denoted by h ) in a Carnot
temperature) cycle is given
W T2 - T1 T
h= = =1 - 1
Second Law of Thermodynamics q2 T2 T2
The second law of thermodynamics tells us whether a given l The above relation was stated in the form of Carnot
process can occur spontaneously and to what extent, it also theorem by Carnot, i.e. “Every perfect engine
helps us to calculate maximum fraction of heat that can be working reversibly between the same temperature limits
converted into work in a given process. The second law states has the same efficiency, whatever be the working
that the entropy of the universe is continuously increasing substance.”
and tends to a maximum.
For an irreversible process,
dq
Third Law of Thermodynamics
dS > l This law was proposed by German chemist Walther
T
Nernst. According to this law, ‘‘The entropy of a perfectly
dq
\ dS ³ crystalline substance approaches zero as the absolute
T zero of temperature is approached’’.
 l It forms the basis from which entropies at other l At equilibrium, DG = 0
temperatures can be measured, lim S = 0 \ DG ° = -2.303 RT log K
T ®0
K = equilibrium constant
Gibbs Free Energy (DG ) l ° F
DG ° = - n Ecell
l The maximum amount of energy available to a system, where, n = number of electrons lose or gained,
during a process that can be converted into useful work is °
Ecell = standard electrode potential,
called free energy or Gibbs free energy.
1F = 96500 C
l Under standard conditions of temperature
(i.e. at 298 K) and pressure (i.e. 1 atm), the free energy l Efficiency of the fuel cell = DG / DH ´ 100
change for a process in which reactants in their standard
state is converted into products in their standard state is
called standard free energy change (i.e. DG°). Thermochemistry
l The changes in the Gibbs energy of a system as a function Thermochemistry is a branch of chemistry which deals with
of temperature can be calculated by the equation known energy exchange between a chemical system and its
as Gibbs Helmholtz Equation. surrounding. Heat is generally evolved or absorbed whenever
a chemical reaction takes place, or change in the state of
DG = DH - TDS matter (vaporisation, fusion, phase transition) occurs.
where, DG = Gibbs free energy (measurement of useful l Thermochemistry focuses on these energy changes,
work)
particularly on the system’s energy exchange with its
l The following cases are considered for DG. surroundings.
(i) DG > 0, for non-spontaneous process l The heat change accompanying chemical reactions or
(ii) DG < 0, for spontaneous process physical changes are measured experimentally with the
(iii) DG = 0, at equilibrium help of calorimeter.
l Chemical Reactions are invariably associated with
Criteria for Spontaneity transfer of energy and most frequently, energy transfer in
l In the determination of spontaneity, Gibbs energy criteria chemical reactions takes place in the form of heat.
is better than entropy criteria because Gibbs energy refers Reactions may be exothermic or endothermic.
to the system only while entropy refers to both system (i) Exothermic reactions transfer heat to the
and surroundings. surroundings.
l For negative value of DG several conditions exist which 4Al (s) + 3O2 (g) ¾® 2Al2O3 (s);
plays an important role in deciding the spontaneity of the DH = - 1676 kJ
process. (ii) Endothermic reactions transfer heat from the
surroundings.
DS DH DG Spontaneity of a Process
N2 (g) + O2 (g) ¾® 2NO (g); DH = + 90.4 kJ
+ - Negative at all Spontaneous at all
temperatures. temperatures.
- - Negative at all
temperatures.
Spontaneous at low
temperature but
Thermochemical Standard State
non-spontaneous at high l A thermochemical standard state of a substance is its
temperature. most stable state under 1 atm pressure (standard
+ + Positive at low Spontaneous at high pressure) and 298 K (standard temperature). Under these
temperature and negative temperature. conditions, any parameter is designated the superscript q
at high temperature. or 0.
+ + Positive at all temperature. Non-spontaneous at all l Purest form for liquids and solids, most stable states are
temperature. considered with 1 bar pressure condition and with 298 K
temperature.
Relation between Gibbs Energy l For a gas, the standard state is considered at a pressure of
one atmosphere. In a mixture of gases, its partial pressure
Change and Equilibrium Constant must be one atmosphere.
Relation between Gibbs free energy with reaction quotient l For a substance in solution, the standard state refers to
and equilibrium constant are as follows : one molar concentration.
l DG = DG °+ 2.303 RT log Q
where, Q = reaction quotient
 e.g. CH 4 ( g ) + 2O2 ( g ) ¾® CO 2( g ) + 2H2O ( l);
Heat or Enthalpy of Reaction
DH c° = -192 kcal mol -1
l It is the amount of heat absorbed or evolved at constant
pressure, when the quantities of substance indicated by l DH combustion is always negative but for certain
thermochemical equation have completely reacted. It is reactions it is positive. For example,
denoted by DH r , e.g. N2 + O2 ¾® 2NO; DH = positive
CH4(g )+ 2O 2(g ) ¾® CO 2(g )+ 2 H2O(g ); DH r = -890.3 1
F2 + O2 ¾® OF2 ; DH = positive
kJ 2
l DH r° = (sum of enthalpies of products) -(sum of enthalpies 3. Enthalpy of Neutralisation (DH n° )
of reactants), i.e. l It is the amount of heat liberated when 1g equivalent of
DH r° = SH products - SH reactants an acid is completely neutralised by 1g equivalent of a
base. DH n is constant for strong acid and strong base,
Standard Enthalpy When reaction is carried out at standard
conditions (i.e. at 1 atm pressure and 298 K) It is denoted as i.e. DH n = -13.7 kcal mol -1 or -57.27 kJ mol -1
by D r H ° . HCl( aq )+ NaOH ( aq ) ¾® NaCl( aq )+ H 2O( l );
(i) If H products = H reactants ; DH = 0 DH n = -57.3 kJ mol -1
(ii) If H products > H reactants ; DH = +ve, reaction is said to l For a weak acid against a strong base or weak base, the
be endothermic. numerical value of DH n is always less than 13.7 kcal due
(iii) If H products < H reactants ; DH = -ve, reaction is said to the fact that here the heat is used up in ionisation of
to be exothermic. weak acid or weak base.
l The absolute value of heat of neutralization of HF is more
Factors Influencing Enthalpy of Reaction than 57.3 kJ. This is due to very high heat of hydration of
fluoride ion.
Various factors that affect the enthalpy of reaction are :
4. Standard Enthalpy of Atomisation (DH a° )
(i) Physical state of reactants and products
(ii)Allotropic forms of elements involved It is the enthalpy change on breaking one mole of bonds
completely to obtain atoms in the gas phase. In case of
(iii)Chemical composition state of reactants and products
diatomic molecules ( X 2 ), the enthalpy of atomisation, bond
(iv)Amount of reactants dissociation enthalpy and bond enthalpy are same thing.
(v) Temperature 5. Lattice Enthalpy (DHlattice )
(vi) Reaction conditions It is the enthalpy change, which occurs when one mole of an
ionic compound dissociates into its ions in gaseous state.
Types of Standard Enthalpy of Reaction NaCl(s) ¾® Na + (g) + Cl- (g); DH lattice
° = - 787 kJ mol-1
Different types of standard enthalpy of reactions are given
below: 6. Enthalpy of Hydration (DHhyd )
1. Standard Enthalpy of Formation (DH °f ) It is the enthalpy change, when one mole of anhydrous or
partially hydrated salt combines with required number of
l It is the standard enthalpy change for the formation of moles of water to form a specific hydrate.
one mole of a compound from its elements in their most
stable state of aggregation. e.g. CuSO 4 ( s) + 5H2O( l) ¾® CuSO 4 × 5H2O ( s);
DH hydration = -78.21 kJ mol -1
C (graphite) + 2H2 ( g ) ¾® CH 4 ( g ); DH °f = -74.8 kJ mol
-1 During dissolution, physical state of the compound changes
while during hydration, there is no change in the physical
l Enthalpy of formation of an element at standard state by state of compound.
convention is taken as zero. e.g. enthalpy of formation of °
Mg, Al, Na, H2 ,O2 etc., is taken as zero. 7. Standard Enthalpy of Solution (DH sol )
l The standard enthalpy of the chemical reaction is given It is the standard enthalpy change, when one mole of
by D r H ° = D f H P° - D f H °R substance dissolves in a specified amount of solvent.
°
Here, D f H °P = standard enthalpy of formation for DH sol = DH lattice - DH hydration
products Integral heat of solution is the enthalpy change when 1 mole
D f H °R = standard enthalpy of formation for reactants of solute is dissolved in a pure solvent to form a solution of
2. Standard Enthalpy of Combustion (DHc° ) desired concentration.
l It is the standard enthalpy change per mole of a l Differential heat of solution is the enthalpy change when
substance, when it undergoes complete combustion. 1 mole of solute is dissolved in such a large volume of
 solution so that no enthalpy change occurs on further
dilution.
Hess’s Law of Constant Heat
l If the solubility of a substance is known at two different Summation
temperatures, the mean molar enthalpy of solution over The enthalpy change in a particular reaction is always constant
this temperature range can be calculated by applying an and is independent of the path by which the reaction takes
equation similar to van’t Hoff equation; place.
log S 1 DH æ 1 1 ö DH
= ç ÷ A
çT - T
B
log S2 2.303 R ÷
è 1 2 ø DH1
DH3
where, S 1 and S2 are solubilities at T1 and T2 DH2
C D
temperatures respectively.
8. Standard Enthalpy of Hydrogenation (DH °hydrogenation ) In other words, the total heat change (DH ) accompanying a
chemical reaction is the same whether, the reaction takes
It is the amount of enthalpy change that takes place when one place in one step or in more steps.
mole of unsaturated organic compound is completely
hydrogenated. According to Hess’s law heat of summation is given as:
°
9. Standard Enthalpy of Dilution (DHdil. ) DH = DH1 + DH2 + DH3
The standard enthalpy change, when 1 mole of a substance is Some applications of Hess’s law are :
diluted to such an extent that on further dilution no heat is
l In determination of heat of formation.
evolved or absorbed is termed as standard enthalpy of dilution.
l In determination of heat of transition.
10. Standard Enthalpy of Transition (DHt°)
l In determination of bond enthalpy
It is the enthalpy change when one mole of the substance l In determination of resonance energy
undergoes transition from one allotropic form to another.
Resonance energy = experimental heat of formation -
S(rhombic) ® S(monoclinic); DH t° = - 13.14 kJ calculated heat of formation
°
11. Standard Enthalpy of Fusion (DH fus )
It is the enthalpy change that accompanies melting of one Bond Energy or Enthalpy
mole of a solid substance. l When a bond is formed between two atoms in gaseous
state to form a molecule, some heat is always evolved
DH °fus = - DH °freez which is called bond energy or bond formation energy.
°
12. Standard Enthalpy of Vaporisation (DH vap )
l Bond dissociation energy is the amount of energy required
to break/dissociate bond of a particular type present in one
It is the amount of heat required to convert one mole of liquid molecule of the compound.
into its vapour state.
l Bond energy is taken as the average value of dissociation
DH vap
° = - DH cond
° energies of same type of bonds present in one mole.
° l Since, a chemical reaction involves the breaking of old
13. Standard Enthalpy of Sublimation (DHsub )
bonds in reactants and formation of new bonds in
At standard conditions, change in enthalpy, when one mole products, the enthalpy change of a reaction,
of a solid substance sublimes is called the standard enthalpy
of sublimation. DH r = Sum of BE of reactants - sum of BE of products
l In a polyatomic molecule containing two or more
Dsub H ° = Dfus H ° + Dvap H °
covalent bonds between same atoms (e.g. CH4 ), the term
14. Enthalpy of Ionisation (DHions ) average bond energy is preferred in place of bond
It is the amount of enthalpy change that take place when one dissociation energy.
mole of a covalent compound on dissolution in water splits to
produce ions in the solution. For CH 4, average BE of C ¾ H bond
- + Bond dissociation energy of CH 4
CH3COOH (aq ) eCH COO (aq) + H (aq);
3 =
4
DH ions = - 55.43 kJ mol -1
l Bond dissociation enthalpy values are negative, if bond
formation occurs whereas bond energy values are
positive, if bond dissociation occurs.

Factor Affecting Bond Enthalpy

There are various factors affecting bond enthalpy which are as q = mcDt = C Dt (Heat capacity, C = mc)
follows: Dt = t final - t initial
1. Size of Atoms where, m is the mass of the substance in grams, c is the
l Smaller the size of atom, more closer the atoms to specific heat and C is the heat capacity.
each other during bonding hence, larger is the bond l For endothermic change, q is positive and for exothermic
enthalpy. e.g. order of bond enthalpy of halogens is change, q is negative.
F ¾ F < Cl ¾ Cl > Br ¾ Br > I ¾ I.
l Bond enthalpy of fluorine is smaller than chlorine
because of the high degree of lone pair repulsions in F2
due to its smaller size. Constant Volume Calorimetry
2. Electronegativity (Bomb Calorimeter)
Larger the electronegativity difference between two atoms, l Heat of combustion is measured by placing a known
more is the polarity in bond and thus, more is the bond mass of a compound in a constant volume bomb
strength as well as bond enthalpy. calorimeter which is filled with oxygen at about 30 atm
pressure.
e.g. F ¾ H > O ¾ H > N ¾ H (Bond enthalpy decreases)
l On ignition of the sample electrically, there is evolution
3. Bond Length of heat which can be calculated by recording the rise in
Shorter the bond length, more is the bond dissociation temperature of water.
enthalpy. l Heat lost by the sample = Heat gained by the water
4. Number of Bonding Electrons qcombustion = - [q water + q bomb ]
= - [mwater ´ cwater + mbomb ´ c bomb ] ´ Dt
As the number of electrons involved in bond increases,
strength of the bond increases. This increases the bond
qcombustion = DEcombustion
enthalpy. (combustion in bomb calorimeter at constant V )
e.g. C ººC > C ==C > C ¾ C (Bond enthalpy decreases) Therefore, DH combustion = DE + Dng RT
l The calorific value of a fuel or food is the amount of heat
in calories or joules produced from the complete
Calorimetry combustion of one gram of the fuel or the food.
l The experimental measurement of the heat change of DHcomb
Calorific value =
reaction or enthalpy change is known as calorimetry. In Molecular mass
laboratory, heat changes in physical and chemical
processes are measured with a calorimeter which is an
insulated container