(5285) Sheet Thermodynamics and Thermochemistry TH e

Thermodynamics & Thermochemistry
1. Thermodynamics
Introduction :
Thermodynamics : The branch of science which deals with different forms of energy & their interconversion.
THERMODYNAMICS
Application of thermodynamics :
In chemistry using thermodynamics
 We can predict feasibility of the reaction that is if two substances are mixed then the reaction
between them will takes place or not.
 If reaction does take place then what are the energy changes involved during the reaction.
 If in a chemical reaction, equilibrium is going to get attained then what will be the equilibrium
concentrations of different reactants & products, can be calculated with thermodynamics.
Limitations of Thermodynamics :
 Laws of thermodynamics are applicable to matter in bulk or on system as a whole, these can not be
applied on individual particles(temperature, pressure, enthalpy etc have meanings only for system
as a whole).
 Using thermodynamics we cannot calculate the time taken for completion of a reaction or for attainment
of chemical equilibrium.
Example-1 : A+B C+ D K1, eq = 103

E+F G+H K2, eq = 10–3
Which of these reaction will attain equilibrium earlier ?
Solution : We cannot predict, because value of equilibrium constant has no relation with time taken to attain
equilibrium.
 More the equilibrium constant K, more will be the concentration of products at equilibrium state.
 Smaller the equilibrium constant K, lesser will be the concentration of products at equilibrium state.
Terms to be used in Thermodynamics :

 System : Part of the universe which is under study for energy changes.
Ex. Air in a room, water in a bottle, any living body.
 Surrounding : Rest of the universe.

 Universe : Universe = System + Surroundings
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 Boundary : Anything which separates system & surroundings is called boundary.

 Boundary can be real or imaginary.
 Boundary can be flexible or rigid
e.g. - air in a flexible balloon (flexible boundary) while air in a room (fixed boundary).
 Boundary can be adiabatic (non-conducting ; q = 0) or diathermic (conducting ; q  0 ;T= 0).
Types of system :
 Open system : System which can exchange energy & matter both with the surroundings.
e.g. : Living systems( any living organism) are open systems, air in an open room ; water flow in
pipe.
 Closed system : System which can exchange only energy but cannot exchange matter with the
surroundings is called closed system.
e.g. : any matter in a closed container ; Heating of water in closed container.
 Isolated system : System which cannot exchange energy and matter both with the surroundings.
e.g. : Water in thermos flask.(Though not a perfectly isolated system but can be taken as, for
small interval of time as the energy exchanges are negligible) ; Hot tea in thermos (few time).
Whole of universe is a perfect isolated system.
Open System Close System Isolated system

 State of a system :
 It means the condition in which the system is present.
 It can be specified/defined by measuring/ specifying some observable/measurable properties of the
system like pressure, volume, temperature, amount of substance, elasticity, heat capacity etc.
e.g. For an ideal gaseous system state of the system can be defined by specifying volume,
temperature and pressure.
 We may have to specify more properties of the system depending on the complexity of the system.
State function (State variables) :
 Property of a system which is dependent only on the state of the system i.e. it is a point function
 It is independent of the path adopted to attain a particular state.
e.g. In Mechanics, Displacement of any object will a state function but distance travelled by the
object will be a path function.
For any thermodynamic system,
Temperature, Pressure, Volume, Total internal energy (E or U), Enthapy(H), Gibbs free energy (G),
Entropy (S) are all state functions.
Cv instead of Cp
e.g.
In the above example the final temperature, pressure, and the volume will be same in both the above ways
but the work involved and the heat exchanged during the processes will be different.
 For a cyclic process the change in state functions must be zero.
 dx  0
 State variables can be extensive or intensive.
 Change in state function are not state function.
Eq. T, V, P, H, G, V, etc are not state function.
 Path function :
 Quantities which are dependent on the path/way the system has achieved a particular state.
e.g. Heat, work, Heat capacities (Molar heat capacities, specific heat capacities etc.).
 These quantities are define when there is a process going on.
 These can not have any definite (particular) value in any particular state of the system.
 Types of properties
Extensive properties :
 Functions or properties of the system which are dependent on mass or on size of the system are
called Extensive Properties .
 Extensive functions are additive in nature (The addition of the volumes of the two parts equals the
volume of the whole of the room.)
e.g. Volume, Mass, Total heat capacity, Total internal energy (E), Enthalpy(H), Gibbs Free
Energy(G), Entropy(S) ; moles etc.
Intensive properties :
 Functions or properties which are not mass dependent or size dependent are called intensive
function.
 Intensive properties are not additive in nature.
eg. Temperature, pressure, molar heat capacity, specific heat capacity, density,concentration, vapour
pressure; B.P. ; F.P. ; Viscosity ; pH etc.
How to identify extensive or intensive properties

If a system in a particular state is divided into two equal or unequal parts, the properties which have value
equal to the original value of that property for the whole of the system is called an Intensive property. While
the properties which have values different from the values for whole of the system are called Extensive
Properties.
 For example consider air in a room at temp of 300K, 1 atm pressure. Now, if the room is divided by
some boundary (imaginary or real) into two parts (equal or unequal) then in these two parts :
The temperature, pressure, density of the gas, concentration of gaseous molecules etc. will have
the same value as that of for whole of the system. (intensive)
While the vol7ume of two parts, mass of gas in two parts, total energy of the gaseous molecules
in the two parts, entropy the two parts etc. will be different from the values of these properties as for
the whole of the system initially. (extensive)
 Thermodynamic equilibrium :
 When there is no change in any observable or measurable property of a system with time then the
system is said to be in thermodynamic equilibrium.
 Thermodynamic equilibrium consist of three types of equilibrium.
(a) Mechanical equilibrium
(b) Thermal equilibrium

(c) Chemical equilirbrium
 Mechanical equilibrium :
There should not be any pressure gradient with time or with space (for any ideal gaseous system, for a liquid
system there can be pressure gradient with space as pressure at the bottom of the container in which a
liquid is filled will be greater than the pressure at the surface of the liquid.) in the system.
 Thermal equilibrium : There should not be any temperature gradient (difference).

Temperature may have different values at different places/locations in a system but it should remain
constant with time.
 Chemical equilibrium : There should not be any concentration gradient of any of the species in
the system.
 Types of thermodynamic process on basis of state/conditions
Thermodynamic process : Any method/process by which system can change its state from one state of
thermodynamic equilibrium to another state of thermodynamic equilibrium.
There can be infinite type of thermodynamic processes, out of these the following are important ones:
1. Isothermal process : T = constant
Ti = Tf
T = 0
2. Isochoric process : V = constant
Vi = Vf
V = 0
3. Isobaric process : P = constant
Pi = Pf
P = 0
4. Adiabatic process : q = constant
or heat exchange with the surrounding = 0(zero)
5. Cyclic Process : A system undergoes a series of changes and comes
back to the initial state.
V = 0
H = 0
 Types of thermodynamics processes on basis of the way the processes are carried out :
Reversible process :
The process that can be reversed by a very small change is known as reversible process.
 If a process is carried out in such a manner so that the system is always in thermodynamic equilibrium
at every stage of the process.
 If the process is carried out such that the difference in driving force and opposing force is infinitesimally
small so that process takes place at infinitesimally slow rate.
Fdriving – Fopposing = F and F  0
 An ideal reversible process will take infinite time to get completed.
 It is carried out infinitesimally slowly.
 Strictly speaking there is no ideal reversible process in universe.
To get an idea of a reversible process we can consider the following system.
An ideal gas is enclosed in a container and a massless piston is put on
the gas on which a pile of sand is placed having particles of negligible
mass. To carry out a reversible expansion we will slowing decrease the
mass of the sand lets say by removing the particles one by one, so the
expansion of the gas will take place at infinitesimally small rate and we
can always assume the system to in thermodynamic equilibrium. So, the
expansion will be of reversible type.
FBD of piston
For piston to be in equilibrium : Pgas = Patm + Mg/A
Sign : i – f : expainsion
f – i : compression
 Irreversible process : The process can not be reversed by a small change is known as irreversible.
 If a process is carried out in such a manner so that the system is in thermodynamic equilibrium
(I) Only at initial & final state of the process but not at the intermediate stages.
(II) System may be in thermodynamic equilibrium state at some finite number of intermediate stages
only - for example - n step irreversible expansion of a gas
 If during the process there is a finite difference in driving force and opposing force so that process
takes place with a finite rate ; Fdriving – Fopposing = F
 Irreversible processes will get completed in finite time.
 At intermediate stages of the irreversible process, different state function such as Pressure,
temperature etc. are not defined.
 All real process are irreversible.
Consider the above system. If the stopper placed over the piston is removed, then the piston will move with
almost infinite acceleration and will keep moving to a position where the pressure of the gas becomes equal
to the external pressure. Since the process will get completed in finite time and there was a finite difference
between the driving force and the opposing force so, process is irreversible.During the process, the pressure
of the gas can not be defined as it will be having different values at different locations.
Sign : i – f : expainsion
f – i : compression
 Modes of energy exchange :
These are two ways by which a system can interact or can exchange energy with its surroundings.
(i) Heat & (ii) Work
Heat & Work both are forms of energy.
Heat : When the energy transfer across a boundary as a result of temperature difference between system &
surroundings is known as heat.
 Modes of heat transfer : Conduction (solids) ; Convection (fluids) ; Radiation (vacuum)
Work : Energy transfer which is not heat or which is not because of temperature difference is called work.
Work can be of many types : Mechanical work, Electrical work, Magnetic work, Gravitational work etc.
The same energy transfer can be called work or can also be called heat depending on choice
of the system.
To understand this, consider a system shown below in which water is taken in a closed container at 25ºC,
the surroundings is also at temperature of 25ºC and there is a heater coil in the dipped in the water which is
connected to a battery through a switch S.Heater coil is also at 25ºC initially.
Now, there are two ways in which system can be chosen.
–System : All contents of the container (water + Heater coil).

When switch is turned on there will be increment in the temperature of the system. Since the temperature
of the surroundings was equal to temperature of the system so, heat can not flow but still there is increment
in the energy of the system and hence, there is temperature increment. This must be because of electrical
work done by the battery on the system not because of the heat transfer as initially temperatures were equal.
–System : Water only is our system. Heater coil will be part of the surroundings.
In this case when switch is turned on the temperature of the heater coil will increase first so there will be a
temperature difference between system & surroundings. Hence, this energy transfer will be called heat.
 IUPAC Sign convention about Heat and Work

Any energy given to system is taken positive so heat given to system = positive
heat taken out from system = Negative
Work done on the system = Positive
Work done by the system = Negative
The sign convention is different from physics, but the meaning always comes out to
be same only in equation we have to use a different sign convention for work.
So if in any problem, w = – 10 J
It means system has done work of 10 Joule on surroundings.
According to Chemistry : According to Physics :
Q Q
w w
U = Q + W U = Q – W
IUPAC convention of Heat

1. Heat given to the system = +ve 2. Heat coming out of the system = –ve
3. Work done on the system = +ve 4. Work done by the system = –ve
Zeroth Law of Thermodynamics (ZLOT) :

 If two systems are in thermal equilibrium with third system,
then they are also in thermal equilibrium with each other.
First Law of Thermodynamics (FLOT) :

Law of energy conservation :
Energy of total universe is always conserved.
or
Total energy of an isolated system is always conserved.
or
Hence absolute value of E can never be calculated only change in value of E can be calculated for a particular
process.
Mathematical form of First Law of thermodynamics.
If a system is initially in a particular state in which its total internal energy is E1. Now q amount of heat is
given to it and w amount of work is done on it so that in new state its total internal energy becomes E2. Then
according to 1st Law of thermodynamics.
E2 = E1 + q + w
so E = (E2 – E1) = q + w
Application of First Law
U = Q + W Since W = – P V
 U = Q – PV
 Calculation of different quantities in First Law of Thermodynamics (FLOT) :

Calculation of E :
Internal Energy (E, also denoted by U) :
Every system having some quantity of matter is associated with a definite amount of energy, called
internal energy.
 It is the sum of all forms of energies present in the system.
E = ETranslational + ERotational + EVibrational + Ebonding + .....
E = EFinal  EInitial .
 Thermodynamic definition of an ideal gas :
 For a gas the internal energy is directly proportional to its absolute temperature then the gas is
termed as an ideal gas.
 E   E 
so   =0,   =0
 V T  P  T
E = qv, heat supplied to a gas at constant volume, since all the heat supplied goes to increase the
internal energy of the gas.
 It is an extensive property & a state function . It is exclusively a function of temperature.
If  T = 0 ;  E = 0 as well.
 With change in temperature only kinetic energy changes.
Degree of freedom  The total no of modes on which a molecule of an ideal gas can exchange energy
during collisons is known as its degrees of freedom.
Translational degree of freedom = 3 (for all type of gases.)
Rotational degree of freedom
=0 – monoatomic gases
=2 – diatomic or linear polyatomic gases
=3 – non-linear polyatomic gases.
If “f” is initial degree of freedom for that gas.
f=3 for monoatomic
=5 for diatomic or linear polyatomic
=6 for non - linear polyatomic
 Law of equipartion of energy :
1
Energy equal to kT is associated with each degree of freedom per ideal gas molecule
2
Where k is Boltzmann constant
1 f
E/molecule = f x kT  E/mole = RT when (R = k × NA)
2 2
 For n moles,
f f
E = nRT only for ideal gas.  E = nRT
2 2
  Calculation of Heat (q)
 Heat is a path function and is generally calculated indirectly using Ist Law of thermodynamics
 First calculate E and W & then q or heat can be calculated if heat capacity of any process is given
to us.
 Total Heat Capacity (CT)
Heat required to raise the temperature of system by 1ºC under the given process is known as total
heat capacity.
dq
Mathematically, CT = J/ºC
dT
 It is extensive properties and path function.
So, dq = CTdT
on integrating 
q  CT dT
 Molar heat capacity (C)

Heat required to raise temperature of 1 mole of a subtance by 1ºC
dq
Mathematically, C = J mole–1 K–1
ndT
So, dq = nCdT
q=  nCdT  nCT
C is intensive path function.
Cp is molar heat capacity at constant pressure
CV is molar heat capacity at constant volume
Cp and CV are intensive but not a path function
 Specific heat capacity (s) :
Heat required to raise temperature of unit mass (generally 1 g) of a substance by 1ºC.
dq
S= Jg–1 K–1
mdT
So, dq = msdT
q=  dq   ms dT msT
S is intensive path function
SP is specific heat capacity at constant pressure
SV is specific heat capacity at constant volume
SP & SV are intensive but not a path function
Total heat capacity, molar heat capacity & specific heat capacity of a process on a substance are related as
CT = nC = ms & C = Ms
Where m – weight of substance
M – molar mass of substance
n – no. of moles of the substance
For isothermal process C =±  For isobaric process C = Cp

For isochoric process C = Cv For adiabatic process C=0
Heat capacity can have value from –  to +  depending on the process.
Note :
(1) Heat capacity is a path function and different type of heat capacities are defined
(2) Remember heat capacity of a substance is not fixed it is dependent on type of process which is being
performed on that substance.
Example-2 : During an expansion of ideal gas the work done by gas is 100 J and the heat capacity of process is
found to be + 2 J/ºC. Find E of gas if the final temperature of gas is 25ºC higher than its initial
temperature.
Solution : E = q + W
q = 2 × 25 = 50 J & W = –100 J
E = 50 – 100 = – 50 J
WORK DONE (w) :

Energy that is transmitted from one system to another in such a way that difference of temperature is
not directly involved is known as work. It is a path function.
This definition is consistent with our understanding of work as dw = Fdx. The force F can arise from
electrical, magnetic, gravitational & other sources.
Units :
Heat & work both are forms of energy . Hence, their units are units of energy. i.e.S system: Joules (J).
Much data is available in the old units of calories (cal) as well.
P × V = (litre. atmosphere) term which has unit of energy . It is useful to remember the conversion
1 litre. atm = 101.3 Joules = 24.206 cal
 For irreversible processes, state parameters such as P,T etc cannot be defined. Hence, work
cannot be estimated using P gas. But by the work energy theorem
W gas = – W ext + Kpisston
When the piston comes to rest again Kpiston = 0
 W gas = – W ext = – P
ext dv
as the external pressure is always defined hence, for all processes work can be calculated using

W gas = – W ext = – Pext .dv = –PextV
 Calculation of work for different type of process on an ideal gas.

1. ISOTHERMAL PROCESS :
(A) Isothermal expansion : There are many ways in which a gas can be expanded isothermally.
(a) Isothermal reversible expansion :
mg
Pext = P0 + =z Pgas = P (always)
A
In reversible process, Pext= Pgas (thermodynamic equilibrium always)
nRT
Since process is isothermal ; P=
V
Vf Vf Vf
nRT
W=
–  Pext dV = –  P dV  W=
–  V
dV
Vi Vi Vi
 Vf 
W = –nRT ln  V 

 i 
Work = Area under the P–V diagram

In expansion work is done by system on the surroundings and Vf > Vi
W = –ve
(b) Irreversible isothermal expansion :
(i) Single step isothermal expansion
We are assuming expansion against atmospheric pressure which need not be the case in a given problem.
A mass equal to m0 is placed on piston initially to maintain equilibrium.
Initially, Pi = Pgas = Patm + m0 g/A
For expansion to take place, m0 mass is suddenly removed so gas expands against constant external
pressure of Patm
In this case, the pressure of the gas will not be defined as the sudden expansion has taken place so all the
molecules of sample will not get the information of expansion simultaneously, there will be a time gap and
hence, there will be a state of turbulence.
From some intermediate state of volume ‘V’, the work done is slight expansion from
V  (V + dV)
dw = – Pext . dV (IUPAC sign convention)
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Vf
So, W=  
dw   Pext .dv = – P (V – V )
Vi
ext f i
Only initial and final states can be located (as at intermediate stages pressure of the gas is not defined)
(ii) Two step isothermal expansion :
Mass M0 is divided into two mass (may be equal or unequal)
M0  (m1  m2 )
Now, if m1 only is removed, then the expansion of gas will take place against constant external
pressure
Pext1 = (Patm + m2g/A)
and this expansion will take place only upto volume V1 such that
Pext1 . V1 = Pi Vi (isothermal)
Now, if second mass m2 is also removed then expansion
V1  Vf will take place against constant pressure
So, Pext 2 = Patm
work done is expansion Vi  V1
W 1 = – (Patm +M2g/A) (Vi – V1)
& work done is expansion V1  Vf
W 2 = – Patm (Vf – Vi)
Total work = W 1 + W 2
Patm
M1
Vf M0
V
Vi
 Work done in this irreversible expansion is greater than work done by gas during the single stage
expansion of gas and so on for three step expansion we divide the mass m0 into three masses m1, m2 and
m3 and remove these step by step and so on.
(iii) For n step expansion and n  

If n   ; Irreversible process becomes reversible process
(B) Isothermal compression of ideal gas :
(a) Reversible isothermal compression of an ideal gas
This can be achieved by placing particles of sand one by one at a very slow take in the assembly
which keeps the temperature of gas constant in this case the expression of work done will be
exactly similar to as obtained in case of reversible expansion of gas
W = – nRT ln(Vf/Vi)
This will automatically come out to be +ve as Vf < Vi
Patm (Patm + M0g/A) = Pf
Vi
Vi
Patm
Vf Vi
(b) Irreversible isothermal compression of an ideal gas
(i) Single step compression :
To compress gas a mass m0 is suddenly placed on massless piston
dw = – Pext. dv = – (Patm + m0g/A) dv
so, to calculate total work done on the gas
Vf
W=  dw   V Pext . dv ;
i
W = – Pext (Vf – Vi)
(ii) Two step compression :

Place mass m0 in two fragments (m1+m2) the
graphical representation will make the calculation
of work done .
If m1 is placed first, then the first compression

has taken place aganist external pressure of
(Patm + m1g/A)
So, W 1 = – (Patm + m1 g/A) (V1 – Vi)
Simlarly, W 2 = – (Patm + m0 g/A) (Vf – Vi)
Note : If process takes place in n steps and n  then process will be like reversible compression.
Conclusion :
Whenever work is done on the gas then it will be minimum in case of reversible process.
Thats why different machines/engines are designed to work reversibly so maximum output can be obtained
but minimum input is given to it.
output – work done by engine/machine/system
input – work done by system us a surrounding
 If expansion/compression takes place against constant external pressure then it is irreversible.

 If there is sudden change then the process is irreversible.
Reversible and irreversible isothermal process. A
 Except the infinite stage compression/expansion, all are irreversible.

 We can redefine reversible and irreversible as follows :
B
Reverssible process : If a process operates is such a fashion that when it is reversed
back both the system as well as surroundings are restored to their initial position w.r.t. both work and heat,
is known as reversible process.
If for the process A  B work = w, heat = Q then if for the process B  A, work = – w, heat = –Q then the
process is reversible.
 If the external pressure is constant in isothermally process, process is irreversible
Example-3 : Calculate the work performed when 2 moles of hydrogen expand isothermally and reversibly at 25ºC
form 15 to 50 litres.
V2 50
Solution : We have, W = – 2.303 n RT log = – 2.303 × 2 × 2 × 298 × log = – 1436 calories.
V1 15
Example-4 : If a gas at a pressure of 10 atm at 300 k expands against a constant external pressure of 2 atm from
a vol. of 10 litres to 20 litres find work done ? [Isothermal process]
Solution : Process is irreversible
20

w  – 2dv  –2 [20 – 10] = – 20 L.atm
10
1 litre atm = 101.3 J
2. ISOCHORIC PROCESS :
Since dv = 0
So, w = 0 (for both reversible and irreversible process)
3. ISOBARIC PROCESS :
Since P = constt. = Pext
So, w = –Pext (vf –vi) (for both reversible and irreversible process)
Calculation of Cp and CV
(a) Constant volume process (Isochoric)
dU = dq + dw
 dU = (dq)v (Heat given at constant volume = change in internal energy)
 dU = (nCdT)v
dU = nCvdT
Cv is Specific molar heat capacity at constant volume.
1 dU 1 d ( fnRT ) / 2 fR
Cv = .  =
n dT n dT 2
(b) Constant pressure process (Isobaric) :
dU = dQ + dW
dU = dQ – PdV
 dQ = dU + PdV ............... (i)
Defining a new thermodynamic function
H  Enthalpy
 It is a state function and extensive property
 It is mathematically defined as :
H = U + PV
as dH = dU + d (Pv)
as P = constant
dH = dU + PdV .............. (ii)
from equation (i) & (ii)
 dH = (dq)p only at constant pressure.
Heat given at constant pressure = Change in enthalpy
dH = (nCdT)p
dH = nCp dT
 Relation between Cp and Cv for an ideal gas
H = U + PV
 dH = dU + d(PV)
for an ideal gas
PV = nRT
d(PV) = d(nRT) = nRdT
nCp dT = nCvdT + nRdT
 Cp – Cv = R only for ideal gas  Mayer’s Relationship
Table # 1 At Normal temperature
Degree of  fR  Cp,m  f  2  R  =  f  2 
S.No. Gas Cv,m   Examples
freedom  2   2   f 
3R 5R 5
1. Monoatomic 3 He ; Ne
2 2 3
5R 7R 7
2. Diatomic 5  N2 ; O 2 ; H 2
2 2 5
Linear 5R 7R 7
3. 5 CO 2 ; HCl
polyatomic 2 2 5
Non-Linear 6R 8R 8 H2O ; NH3 ;
4. 6
polyatomic 2 2 6 CH 4
Note :- At high temperature vibrational degree of freedom is also included.

4. ADIABATIC PROCESS :
dQ = 0 (no heat changed b/w system and surrounding
dU = dQ + dW
nRT
 nCV dT = – PdV   nc V dT 
 
V
. dv
T2 V2
C v .dT R T2 V2
  T
=–  V . dV
V1
 Cv ln T = – R ln V
1 1
T1
R / c v  1
T2  V2   T2   V1 
ln T = ln        
1  V1   T1   V2 
T2 V2 –1 = T1 V1 –1 or T V–1 = constant

PV = constant
 –1
 This is only valid when the quantity PV or TV is constant only for a quasi-static or reversible
process.
 For irreversible adiabatic process these equations are not applicable.
Operation of adiabatic process
(a) Reversible Adiabatic
 Operation wise adiabatic process and isothermal
process are similar hence all the criteria that is
used for judging an isothermal irreversible
processes are applicable to adiabatic process.
 Also, volume in case of isothermal volume is more
than that of adiabatic at constant pressure and
no of moles, V  T
K
w=–  Pext. dv , but Pext = Pint =
V
K V   1
2  V1  1  P2 V2 .V21   P1V1 .V11 
w=– V 
. dv , W = – K
1    =
 1
P2 V2  P1V1
 work done = (as K = P2V2 = P1V1 )
 1
(b) Irreversible Adiabatic

 Adiabatic irreversible expansion –

W =  Pext.dv = – Pext (V2 – V1) , and  du   dw
 W = u
nR(T2  T1 ) P2 V2  P1V1 )
W = nCv (T2 – T1) = =
 1  1
Note: If two states A and B are connected by a reversible path then they can never be connected by an
irreversible path.
If the two states are linked by an adiabatic reversible and irreversible path then
wrev. = urev.
But as u is a state function
 urev. = uirrev.  wirrev. = wrev.
as work is a path function.
If we assume that
wirrev. = wrev.  It implies that
urev.  uirrev.. which again is a contradiction as U is a state function.
 Two states A and B can never lie both on a reversible as will as irreversible adiabatic path.
 There lies only one unique adiabatic path linkage between two states A and B.
 Comparison of Adiabatic Expansion (single stage Vs Infinite stage)
Single stage means irreversible process
Infinite stage means reversible process
In adiabatic compression process,
(W gas)rev < (W gas)irrev urev. < uirrev.
 (T2)rev. < (T2) irrev
(P2)rev.< (P2) irrev (If volume change are same)
(V2)rev.< (V2) irrev (If pressure change are same)
 Comparison of single stage Vs two stage expansion(adiabatic).

If the expansion is carried out in two stages then work done in two stage by the gas > work done in
one stage by the gas. So, Utwo stage > Usingle stage
 Tf in two stage < Tf in single stage because decrease in internal energy in two stage is >
decrease in internal energy in one stage.
Adiabatic Irreversible process (calculation of state parameters)
irrev
State A   State B
P1,V1,T1 P2,V2,T2
nR(T2  T1 ) P2 V2  P1V1 P1V1 P2 V2

W=  = – Pext. (V2 – V1) , =
 1  1 T1 T2
   Free expansion –
Always going to be irrerversible and since Pext = 0
So, dW = – Pext . dV
=0
If no heat is supplied q = 0
then E = 0 So, T = 0.
 Calculation of H, U, work, heat etc.
Case - I For an ideal gas undergoing a process.
the formula to be used are
f
dU = nCvdT = nRdT
2
f 
dH = nCpdT =  2  1 nRdT
 
W=– Pext . dV
dH = dU + d (PV)
du = dQ + dw
Example-5 : Calculate the maximum work done when pressure on 10 g of hydrogen is reduced from 20 atm to
1 atm at a constant temperature of 273 K. The gas behaves ideally. Will there be any change in
internal energy? Also,calculate ‘q’.
P1
Solution : We have, W = – 2.303 nRT log P
2
wt. in grams 10
n = number of moles of hydrogen = mol. wt.
= = 5 moles.
2
20
Thus, W = – 2.303 × 5 × 2 × 273 × log = – 8180 calories.
1
Further, the change in state of the system at constant temperature will not change internal energy
i.e., U = 0.
Again, q = U – W = 0 – (– 8180 ) = 8180 calories.
Case - II For solids and liquid system :

f
dU = nCvdT  nRdT (as it is not an ideal gas)
2
f 
dH = nCp dT    1 nRT (as it is not an ideal gas)
2 
W=– Pext . dV
H = U + (P2V2 – P1V1)
dU = dq + dw
Example-6 : A liquid of volume of 100 L and at the external pressure of 10 atm–Lt the liquid is confined inside an
adiabatic bath. External pressure of the liquid is suddenly increased to 100 atm and the liquid gets
compressed by 1 L against this pressure then find,
(i) work (ii) U (iii) H
Solution : Work done = –100 × – 1 = 100 L. atm
q = 0 w = U
 100 = U
H = U + (P1V2 – P1V1 )
= 100 + (100 × 99 – 100 × 10)
= 100 + 100 × 89 = 9000 lit atm.
1 L. atm = 101.3 Joule.
Case - III For chemical reactions :

aA (s) + bB() + cC(g) a’A’(s) + b’B’ () + c’ C’ (g)

W = – Pext . dV
=   Pext. Vf  Vi 
= – Pext. [(VA’(s) + (VB’() + (VC’(g)– (VA(s) + (VB() + (VC(g)]
 W = – Pext. [VC’(g) – VC(g)]

 n'c RT nc RT  Pext . (n'c nc )RT
= – Pext.  P  =–
 ext Pext  Pext .
W = – (n’c – nc)RT
 W = – ng RT
dU = dq + dw
if at constant pressure
dq = dH
 dU = dH – pdV
dU = dH – ng RT
 dH = dU + ng RT
Example-7 : For the combustion of 1 mole of liquid benzene at 25ºC, the heat of reaction at constant pressure is
1
given by, C6H6() + 7 O (g)  6CO2 (g) + 3H2O (); H = –780980 cal.
2 2
What would be the heat of reaction at constant volume?
Solution : We have, H = E + ng RT
Here, ng = 6 – 7.5 = – 1.5.
Thus, E = H – ng RT = – 780980 – (–1.5 ) × 2 × 298 = – 780090 calories.
Case - IV During phase transformation.

Phase transitions generally take place at constant pressure (unless specified) and at constant temperature.
So, T = 0
But still H and E are non zero (different from process on an ideal gas)
Because during phase transitions though the kinetic energy of molecules of substance remains same but
the potential energy gets modified or changed and since E is summation of all type of energies. So, E  0.
Also, during this phase transition (PV)  0
Hence, H  0.
Now, to calculate heat – generally latent heats of transitions are given and since process is taking place at
constant pressure. So, q = H.
To calculate W, use dW = – Pext dV and then calculate E using Ist law of thermodynamics.
Example-8 : Calculate q, W, E and H when 100 g of CaCO3 is converted into its aragonite form given density
of calcite = 2 g/cc and density of aragonite = 2.5 g/cc
Solution : CaCO3 CaCO3
Calcite Aragonite H = 2 kJ/mole
Generally for solid  Solid
solid  Liquid
solid  Liquid
transitions W << q So, E ~  q = H
while for gaseous conversion for example
Solid  gas
Liquid  gas
q = H  E, as W will be significant
S.No. Process w q U H Molar heat capacity

1. Isochoric 0 nCv,m  Tf  Ti  qv nCp,m  Tf  Ti  Cv,m
2. Isobaric Pext  V2  V1  nCp,m  Tf  Ti  q + w nCp,m  Tf  Ti  Cp,m

V 
Wrev  nRT ln  f 
3. Isothemal  Vi  –w 0 0 ± 
Wirrev  Pext  Vf  Vi 
Pf Vf  PV
i i
4. Adidatic 0 w 0 0
 1
Pf Vf  PVi i R
5. Polytropic U – w nCv,m (T2–T1) nCp,m(T2 – T1) Cv,m+
(n  1) 1 
 IInd Law of thermodynamics :

Requirement : Ist law insufficient to Explain
Neutralization, Melting of ice > 0°
Combustion, Freezing of water < 0°
Fall of water, Boiling of water > 100° C
Cooling of a hot body, Free expansion of a gas, mixing of gases.
Spontaneous /Natural /Irreversible Processes :
If a system moves along in a direction on its own and system, surrounding interactions without the help of
any external agency, then that direction is known as spontaneous direction and the process is knwon as a
spontaneous process.
Limitation :
First law cannot predict the direction of any process. But in nature a process is found to have a specific
direction at certain conditions.
1. Energy can be the factor : To achieve stability
* All exothermic processes are spontaneous.
* All endothermic processes are non spontaneous.
Exceptions
* melting of ice (above 0°C) although H > 0 , E > 0
* Vaporization of water (above 100°C) H > 0 , E > 0
* Spreading of ink in water H = 0 , E = 0
* Mixing of two gases
* Endothermic solution of salt H > 0 , E > 0
2. It is observed that nature tries to distribute energy and matter uniformaly (randomization)
Second law of thermodynamics :
Entropy of the universe is constantly inereasing.
S universe = S system + S surrounding > 0 for a spontaneous process.
Where (S) = entropy is the measure of randomness or disorder. It is a state function and extensive property.
Mathematically
dq rev dq rev dq
ds =
T
or S =  T
,
T
is state function only for reversible process
1
dS  dqrev , dS 
T
At Higher T - entropy is already high. Therefore, heat addition will not introduce much change in the entropy.
  Entropy Calculation :
 Calculation of Ssystem
As ‘S’ is a state function. Hence ’S’ will also be a state function.

 S irrev = S rev
B
dqrev
S = 
A
T reversible path
 Entropy calculation for an ideal gas undergo in a process.

S
irr
State A 
 State B
P1, V1, T1 P2, V2, T2
As ‘S’ is a state function.So, S will not depend upon path
B
dq rev
Sirrev = Srev, system = 
A
T rev path.
from the first law

dU = dQ + dw
dQ = dU – dw
for reversible path
dq = dqrev
dqrev = dU + Pgas dV {Pext = Pgas reversible}
B
dU  Pgas dV
Srev, system = 
A
T
for an ideal gas

Pgas nR
 & du = ncV dT
T V
T2 V2
nc v dT nRdV
 S sys =  T
  V
T1 V1
T2 V2
 Ssystem = ncv n T + nR n V
1 1
   Calculation of Ssurrounding : As the surrounding is an infinite heat reservoir hence, no. amount of heat given
to the surrounding can cause turbulance in it, hence all heat exhanges with surroundings are considered to
be reversible.
dqsurrounding
Ssurrounding =  T
For surrounding T is constant
1 qsurrounding
 Ssurr =
T  dq surr =
T
But according to the law of conservation of energy
qsurr = – qsystem
 q system
 Ssurr =
T
 Isothermal process :
(a) Reversible
Re v
State A  State B
P1,V1,T P2,V2,T
T2 V
S system = nCVn + nRn 2
T1 V1
Since T1 = T2
V2
S system = nRn
V1
q system
Ssurrounding = 
T
du = dq + dw (since T1 = T2 . So, du = 0)
 dq = – dw
V2
 q = –w as w = – nRTn V
1
V2
q = nRTn V
1
V2
 nRTn
V1 V2
 Ssys. =  –nRn
T V1
Suniverse= Ssystem + Ssurr
V2 V2
= nRn –nRn =0
V1 V1
(b) rreversible
irrev
P1,V1,T P2,V2,T
V2
Ssystem = nRn
V1
 qsystem
SSurrounding =
T
qsystem is calculated using FLOT
qsystem = Pext(V2– V1)
p ext ( V2  V1 )
Ssurrounding =
T
V2 p ext ( V2  V1 )
Suniverse = nRn –
V1 T
1  V2 
= (nRT n )  Pext ( V2  V1) = 1 [W – W ] > 0
T  V1  T irrev rev
As irreversible work of gas is more than reversible work.

 Adiabatic Process (Isoentropic process)
(a) Reversible Adiabatic
rev
P1,V1, T1 P2,V2, T2
T2 V2
Ssystem = nCV n T + nR n V
1 1
TV–1 = constant
 1
T2  V1 
=  
T1  V2 
 1
 V1  V2
(S)system = nCVn   + nRn V = 0
 V2  1
q sys
S surr = – = 0 (qsys= 0)
T
S universe = 0 + 0 = 0
(b) Irreversible Adiabatic
irre
P1,V1,T1 P2,V2,T2
Using irreversible adiabatic process it is not possible to reach same state B which was reached by
reversible adiabatic.
T2 V2
S system = nCV n T + nR n V > 0 [(T2)irrev > (T2)rev]
1 1
q sys
S surr = – =0 as q = 0
T
For irreversible expansion the decrease in temprature will be lesser as work done is lesser hence, decrease
in entropy due to fall in temprature will be lesser in case of irrversible expansion. Hence, net entropy would
increase.
 Isobaric process :
(a) Reversible Isobaric
rev
P, V1, T1 P, V2, T2
dqrev nCp dT T2
Ssys =  T
=  T
= nCpn T
1
2 T
dqrev – dqsys T2
Ssurrounding =
T  =
T
T  = – nCpn T
1
1
Suniverse = Ssys + Ssurrounding = 0

(b) Irreversible Isobaric
T2
dqrev nC p dT T2
Ssys =  T
= 
T1
T = nCpn
T1
– nCp T2 – T1 
Ssurrounding =
T2
Suniverse = Ssys + Ssurrounding > 0
 Isochoric Process
(a) Reversible Isochoric
rev
State A 
 State B
P1,V, T1 P2,V, T2
T2
dqrev nC v dT T2
Ssys =  T
= 
T1
T = nCvn T
1
T2
dqrev – dqsys T2
Ssurrounding =
T =
T1
T 
= – nCvn T
1
Suniverse = Ssys + Ssurrounding = 0

(b) Irrversible Isochoric
T2
dqrev nC v dT T2
Ssys =  T
= 
T1
T = nCp
n
T1
– nC v T2 – T1 
Ssurrounding = T2
Suniverse = Ssys + Ssurrounding > 0
 Entropy Calculation for phase transformations

dq 1 Q
Sfusion= T 
T  dq  T
Hfus
for constant pressure Sfus. =
T
Ufusion
for constant volume Sfus. =
T
dq 1 Q
Svap = T 
T  dq  T
H vap
for constant Pressure, Svap =
T
U vap
for constant Volume, Svap =
T
 Entropy Calculation solid or liquid systems:
(a) ‘Cu’ block kept in open atmosphere
T2
msdT T2
Ssystem = 
T1
T = mn T1
dqsurr q surr
 Ssurr =  T

T2
but q surr = – qsystem = – ms (T2 – T1) = ms (T1 – T2)
ms (T1 – T2 )
Hence, Ssurr =
T2
Suniverse = Ssystem + Ssurr
T2 ms (T1  T2 )
 Suniverse = ms n T + T2
>0
1
(b) Two copper block kept in contact in thermostat

Two blocks are of same mass
Ssurr = 0 (since no heat is lost to surrounding)
S system = SA + SB
System will reach a common temperature (Tf )
and T1 > Tf > T2
Tf Tf
dq A dqB
S system = 
T1
T + 
T2
T
Tf Tf
msdT msdT  Tf Tf 
= 
T1
T + 
T2
T = ms n  n
 T1

T2 
2
Tf
Ssystem = msn
T1T2
T1  T2 T1  T2 2
Since Tf =  Ssystem = msn
2 4T1T2
Example-9 : (a) One mole of an idal gas expands isothermally and reversibly at 25ºC from a volume of 10 litres to
a volume of 20 litres.
(i) What is the change in entropy of the gas?
(ii) How much work is done by the gas?
(iii) What is q (surroundings)?
(iv) What is the change in the entropy of the surroundings?
(v) What is the change in the entropy of the system plus the surroundings?
(b) Also answer the questions opening a stopcock and allowing the gas to rush into an evacuated
bulb of 10 L volume.
V2 20
Solution : (a) (i) S = 2.303 nR log V = 2.303 ×1 × 8.314 × log = 5.76 J/K.
1 10
V2
(ii) W rev = –2.303nRT log V
1
20
= –2.303 × 1 × 8.314 × 298 × log = –1781 J.
10
(iii) For isothermal process, U = 0 and heat is absorbed by the gas,
qrev = U – W = 0 –(–1718) = 1718 J.
 qrev = 1718 J. ( process is reversible)
1718
(iv) Ssurr= – = – 5.76 J/K.
298
As entropy of the system increases by 5.76 J, the entropy of the surroundings decreases by 5.76J,
since the process is carried out reversibly.
(v) Ssys + Ssurr = 0..... for reversible process
(b) (i) S = 5.76 J/K, which is the same as above because S is a state function
(ii) W = 0 ( pext = 0)
(iii) No heat is exchanged with the surroundings.
(iv) Ssurr = 0.
(v) The entropy of the system plus surroundings increases by 5.76 J/K, as we expect entropy
to increase in an irreversible process.
 Third Law Of Thermodynamics :

The entropy of perfect crystals of all pure elements & compounds is
zero at the absolute zero of temperature.
Thus, absolute value of entropy unlike the absolute value of enthalpy for
any pure substance can be calculated at any given temperature. In standard
state (298 K, 1 atm), it is standard absolute entropy Sº.
T
nCdT
S = ST(K)– S0(K) = 
0
T
 For chemical reaction

aA + bB  cC + dD
S0system = ( ni S0m )product – ( ni S0m )reactant
where S0m = standard molar entropy. It can calculated using third law of thermodynamics.
 Q system  Hsystem
Ssurr = =
T T
* For a perfactly crystline substance at 0 K, entropy = 0
 For phase transformations

dp 1 Q
Sfusion= T 
Tdp 
T
Hfus
for constant pressure Sfus. =
T
Ufusion
for constant volume Sfus. =
T
dQ 1 Q
Svap = T 
TdQ 
T
H vap
for constant Pressure, Svap =
T
Uvap
for constant Volume, Svap =
T
 Gibb’s free energy (G) :
A system parameter to predict the spontaneity of chemical reaction was introduced by Gibb’s so
that entropy calculation for the surrounding need not be carried out.
It is a free energy at constant pressure.
G = H – TS
dG = dH – TdS – SdT
& H = U + PV
dH = dU + PdV + VdP  dG = dU + PdV + VdP –TdS –SdT
From Ist law of thermodynamics
dq = dU + PdV
& from 2nd law, dq = TdS
dG = dq + VdP –TdS – SdT
dG = – SdT + VdP
At constant temperature,
dG = VdP
nRT
For ideal gas, V =
P
RT
dGm = VmdP = dP
P
2 P2
dP
 dG m = RT 
P1
P
1
P2
Gm 2 – Gm1 = RTn
P1
Where Gm is free energy for 1 mole
If Gm1 is free energy for 1 mole in standard state and Gm2 is free energy for one mole in any other state.
P P
Gm – G°m = RTln & G – G° = nRTn
1 1
For the reaction, aA(g) + bB(g) C(g) + dD(g)
(G)reaction = (G)product – (G)reactant
(G)reaction = GC + GD – GA – GB
PC
GC – G°C = cRTln  GC = G°C + cRTln PC
1
Similarly, GD= G°D + dRTln PD ; GA= G°A + aRTln PA , GB= G°B + bRTln PB
(G)reaction = (G°C + cRTln PC) + (G°D + dRTln PD ) – (G°A + aRTln PA ) – (G°B + bRTln PB)
P c C .P dD
= (G)°reaction + RTln
P a A .P bB
Greaction = G°reaction + RTlnQ
Gibb’s Helmholtz Equation :

dG = VdP – SdT
At constant Pressure
 dG   G 
dG = – SdT    =–S&   = – S
 dT P  T  P
G–H
& G = H – TS  =–S
T
G–H  G 
=  
T  T P
 G 
G = H + T 
  T P
 G 
G = H + T  
 T  P
G = H –T S
Suniverse = Ssystem + Ssurrounding

 Q system  Hsystem
Ssurr = =
T T
TS univ = TS system – Hsystem
Introducing a new thermodyamic function G = Gibb’s free energy (State function and an extensive
property)
Gsystem = H system – TS system
 G = H – TS
Gsystem = H system – TS system .................. (ii)
Comparing equation (i) and (ii)
Gsystem = – TS universe
New criteria of spontaneity :
(i) If G system is (–ve) < 0  process is spontaneous
(ii) If G system is > 0  process is non spontaneous
(iii) If G system = 0  system is at equilibrium
So, at every temparature G  0
H system S system G system = H system – TS system
+ Ve – Ve +
– Ve + Ve –
+ Ve + Ve – Ve at high temprature
– Ve – Ve + Ve at high temprature
Gº = standrad free energy change :
When the reactants under standrad conditions gets converted into products which is also under standared
condition, then the free energy change is known as Gº (it is a constant) for 1 mole at 1 bar.
At standared conditions :
G° = H° – TS°
= constant for a GIVEN REACTION
AB  C +  D
G° = (Gbb’s energy of product) – (Gibb’s energy of reactant)
0 0 0 0 0 0
G° =  Gm ,C + Gm,D – Gm, A –  Gm,B , where Gm can not be calculated as Hm cannot be
calculated.
hence, we can convert this relation in to Gibb’s energy of formation of substance.
G° = G0f ,C + G0f ,D – G0f ,A – G0f ,B
G0f : standared Gibb’s energy of formation.
G0f (elements in their standard states) = 0
G° = G0f ,product – G0f,reac tan ts
For a reaction in progress
G = Gº + RT n Q
Q is reaction quotient , G > 0 backward is feasible , G < 0 forward is feasible
At equilibrium G = 0  Q = K  Gº = – RT n K at equilibrium
Example-10 : Ka for CH3COOH at 25ºC is 1.754 × 10-5 . At 50ºC, Ka is 1.633 × 10-5 What are Hº and Sº for the
ionisation of CH3COOH?
Solution : (Gº)298 = – 2.303RT log K = – 2.303 ×8.314 × 298 ×log (1.754 ×10-5) = 27194 J.
(Gº)323 = 2.303 × 8.314 × 323 × log ( 1.633 × 10-5) = 29605 J.
Gº = Hº – TSº
27194 = Hº – 298 Sº
29605 = Hº – 323 Sº
 Hº = – 1.55 kJ/mol
Sº = – 96.44J/mol.K
2. Thermochemistry
 Enthalpy of a substance :
   Every substance has a fixed value of enthalpy under any particular state. Though, its exact value cannot be
calculated but it has some finite fixed value.
   The enthalpy of one mole of a substance called molar enthalpy in any particular state can be assigned symbol
   Hm(substance) : For example molar enthalpy of water vapours at 398 K and 1 atm pressure may be represented
as Hm (H2O, g, 398 K, 1 atm). In very simple words, enthalpy can be considered as heat constant (amount)
of substance, and during reaction this heat is being released or absorbed.
   Molar enthalpy of substance under standard conditions is called standard molar enthalpy of a substance.
Standard state of any substance means.
 For a GAS standard state means ideal gas at 1 bar partial pressure at any give temperature.
 For a LIQUID – pure liquid at one bar pressure at 1 bar pressure at any given temperature.
 For a PURE CRYSTALLINE SOLID – pure crystalline solid at 1 bar pressure and at any given temperature
 For any SUBSTANCE or ION IN SOLUTION – the species should be in unit molality (can also be taken
as 1M concentration), at one bar pressure and at any given temperature.
   Molar standard enthalpy of water vapours at 398 K will be represented as H°(H2O, g , 398 K) and molar
standard enthalpy of liquid water at 398 K will be represented as Hm° (H2O, l, 398 K)
(It is hypothetical but can be calculated).
   We cannot exactly calculate enthalpy content of a substance only the change in enthalpy can be calculated
when substance is taken from one state to other.
For example :
0 0
Let enthalpy content initially be Hm ,1 & finally enthalpy content be Hm , 2
0 0
Then, H° = Hm , 2 – Hm ,1
= heat added at constant pressure to change temperature from 25°C to 50°C.

= CPT = (18 cal/mole °C) (25°C) = 450 cal
Example-11 : Why does heat get released/absorbed during chemical reactions?

Solution : Because the reactants have a fixed enthalpy content before the reaction and when these are converted
into the products which have a different enthalpy content. So, heat gets released or absorbed. Even
if temperature of reactions remains constant yet due to change in bonding energies E  0.
If Hproducts > Hreactants
Reaction should be endothermic as we have to give extra heat to reactants to get these converted
into products
and if Hproducts < Hreactants
Reaction will be exothermic as extra heat content of reactants will be released during the reaction.
Enthalpy change of a reaction : 
H°reactions = H°products – H°reactants
= positive – endothermic
= negative – exothermic
 Enthalpy of formation :
It is not possible to determine the absolute value of the molar enthalpy of a substance. However, based on
the following convention, the relative values of standard molar enthalpies of formation of various substances
can be built.
  “The standard enthalpy of formation of every element in its stable state of aggregation at one bar pressure
and at specified temperature is assigned a zero value”.The specified temperature is usually taken as 25°C.
A few exmaples are Hf° (O2 , g) = 0
Hf° (C, graphite) = 0 Hf° (C, diamond)  0
Hf° (Br2 , liquid) = 0
Hf° (S, rhombic) = 0 Hf° (S, monoclinic)  0
Hf° (P, white) = 0 Hf° (P, black)  0
“The standard enthalpy of formation of a compound is the change in the standard enthalpy when one mole
of the compound is formed starting from the requisite amounts of elements in their stable state of aggregation”.
The chemical equations corresponding to enthalpy of formation of few substances are given below.
1 1
Enthalpy of formation of HBr(g) : H2 (g) + Br2 (  )  HBr(g)
2 2
0
1 0 1 0
Hf°(HBr, g) = Hm (HBr, g) – H (H , g) – Hm (Br2,  ) ...(1)
2 m 2 2
Enthalpy of formation of SO2 (g) : S (rhombic) + O2 (g)  SO2 (g)
0 0 0
Hf° (SO2, g) = Hm (SO2, g) – Hm (S, rhombic) – Hm (O2, g) ...(2)
But above equations cannot be for calculation of enthalpy of reaction as the molar enthalpies of different
species can not be exactly known.
 Enthalpy of Reaction from Enthalpies of Formation:
The enthalpy of reaction can be calculated by
Hr° =  B Hf°,products –  B Hf°,reactants
B is the stoichiometric coefficient
above equation holds good for any

reaction as the same reference state is
used for reactants and products (shown
in figure).
Example-12 : Calculate the standard enthalpy of reaction ZnO(s) + CO(g)  Zn(s) + CO2 (g).
Given, Hf° (ZnO, s) = – 350 KJ/mole, Hf° (CO2, g) = – 390 KJ/mole, Hf° (CO, g) = – 110 KJ/mole.
Solution : H° = {Hf°(CO2, g) –Hf° (ZnO, s) +Hf° (CO, g))}
H°reaction = –390 –(–350 –110) = 70 KJ
 Hess’s Law of constant heat summation :

   The heat absorbed or evolved in a given chemical equation is the same whether the process occurs in one
step or several steps.
   The chemical equation can be treated as ordinary algebraic expressions and can be added or subtracted to
yield the required equation. The corresponding enthalpies of reactions are also manipulated in the same way
so as to give the enthalpy of reaction for the desired chemical equation.
   Since rH stands for the change of enthalpy when reactants (substances on the left hand side of the arrow)
are converted into products (substances on the right hand side of the arrow) at the same temperature and
pressure, if the reaction is reversed (i.e., products are written on the left hand side and reactants on the right
hand side), then the numerical value of rH remains the same, but its sign changes.
   The utility of Hess’s law is considerable. In almost all the thermochemical numericals, Hess’s law is used.
   One of the important applications of Hess’s law is to determine enthalpy of reaction which is difficult to
determine experimentally. For example, the value rH for the reaction
1
C(graphite) + O (g)  CO(g)
2 2
which is difficult to determine experimentally, can be estimated from the following two reactions for which rH
can be determined experimentally.
C(graphite) + O2(g)  CO2(g) rH1
1
CO(g) + O (g)  CO2(g) rH2
2 2
Substracting the latter from the former, we get
1
C(graphite) + O (g)  CO (g)
2 2
Consequently, rH = rH1 – rH2
Example-13 : Calculate heat of the following reaction at constant pressure,

F2O(g) + H2O(g)  O2 (g) + 2HF(g)
The heats of formation of F2O (g), H2O(g) and HF (g) are 5.5 kcal, –57kcal and –64 kcal respectively.
1
Solution : Given that (i) F2(g) + O (g)  F2O(g); H = 5.5 kcal
2 2
1
(ii) H2(g) + O (g)  H2O(g); H = – 57 kcal
2 2
1 1
(iii) H2(g) + F2(g)  HF(g); H = – 64 kcal
2 2
F2O and H2O in eqns. (i) and (ii) and in the eqn. given in the problem are on the opposite sides, while
HF in eqn. (iii) and in the eqn. given in the problem is on the same sides.
Thus applying, [– Eqn. (i) –Eqn. (ii) + 2 × Eqn. (iii) ], we get
1 1
–F2 (g) – O (g) – H2 (g) – O2(g) + H2 + F2 (g)  –F2O (g) – H2O(g) + 2HF(g);
2 2 2
H = – 5.5 – (– 57) + 2 × ( – 64)
or F2O (g) + H2O (g)  O2 (g) + 2HF(g); H = – 76.5 kcal.
 Relation between energy and enthalpy of a reaction :
 rH =  rU + (vg)RT
where v g is the change in the stoichiocmetric number of gaseous species in going from reactants to
products.
It should be noted that while computing v g of a reaction, only the stoichiometric numbers of gaseous is
counted and those of liquids and solids are completely ignored.
Kirchoff’s equation (Variation of Hº with temprature)
Since the enthalpy (or standard enthalpy) of a substance is dependent on state of the substance, value of
enthalpy of a substance changes with temperature and hence the enthalpy change of reaction is also
dependent on temperaturte at which the reaction is being carried out. This change is enthalpy change (or E,
of reaction is carried out at constant volume) is represented by Kirchoff’s Equations.
P + Q  R + S
at temperature T1 let the standard enthalpy of reaction be H°1 , then
H1° = H°m (R,T1) + H°m (S, T1) – H°m (P, T1) – H°m (Q, T1)
If the same reaction is carried out at temperature T2, then
H2° = H°m (R,T2) + H°m (S, T2) – H°m (P, T2) – H°m (Q, T2)
Then, the change in enthalpy (or difference in enthalpy at these two temperatures)
H° = H2° – H1° =  {Hm° (R,T2) – Hm° (R,T1)} + {Hm° (,T2) – Hm° (,T1)}
–  {Hm° (P,T2) – Hm° (P,T1)} -  {Hm° (Q,T2) – Hm° (Q,T1)}
Hm° (R, T2) – Hm° (R,T1) = CP, R (T2 – T1) = Heat required at constant pressure to increase temperature of one
mole of R from T1 to T2
Similarly
Hm° (S,T2) – Hm° (S,T1) = CP,S (T2 – T1)
Hm° (P,T2) – Hm° (P,T1) = CP,P (T2 – T1) and
Hm° (Q,T2) – Hm° (Q,T1) = CP,Q (T2 – T1)
so H° = H2° – H1° =  CP,R (T2 – T1) + CP,S(T2 – T1) –  CP,P (T2 – T1) – CP,Q(T2 – T1)
= [ CP,R + CP,S –  CP,P – CP,Q] (T2 – T1) = CP (T2 – T1)
CP = CP, R + CP,S – CP,P – CP,Q
= Difference in molar heat capacities of products and reactants.
so H2° = H1° +
 C .dT
P
For example for the reaction

N2 (g) + 3H2 (g)  2NH3 (g)
H2° = H1° + CP (T2 – T1)
where CP = 2CP,NH3  CP,N2  3CP,H2
0 0
* for a constant volume reaction, E 2  E1  C V .dT
 Enthalpy of Combustion :
   It is the enthalpy change when one mole of a compound combines with the requisite amount of oxygen to
give products in their stable forms.
For example, the standard enthalpy of combustion of methane at 298 K is – 890 kJ mol–1. This implies the
following reaction :
CH4 (g) + 2O2(g)  CO2(g) + 2H2O () H° = – 890 kJ mol–1
The standard enthalpy of combustion of methane at 298 K may be written as
Hc° (CH4, g, 298 K) = – 890 kJ mol–1
   The data on the enthalpy of combustion can be determined experimentally.
   With the help of such data, we can determine the enthalpy of formation of a compound, which otherwise is
difficult or impossible to determine experimentally. Consider for example, the enthalpy of formation of CH4(g):
C(graphite) + 2H2(g)  CH4(g)
First of all, the combination of carbon and hydrogen does not occur readily. Secondly, if the reaction is even
completed, the end product would not be pure methane. Therefore, the enthalpy of formation of methane can
be determined indirectly through the enthalpy of combustion of methane :
CH4(g) + 2O2(g)  CO2(g) + 2H2O()
HC°(CH4, g) = Hf°(CO2, g) + 2Hf°(H2O , ) – Hf° (CH4, g)
therefore Hf°(CH4, g) = Hf°(CO2, g) + 2Hf°(H2O , ) – HC° (CH4, g)
   The enthalpies of formation of CO2 and H2O can be determined experimentally by the combustion of carbon
(graphite) and hydrogen. Thus, knowing the mesured value of HC°(CH4, g), the enthalpy of formation of CH4
can be calculated. The value is
Hf°(CH4, g) = Hf°(CO2, g) + 2 Hf°(H2O , ) – HC° (CH4, g)
= [– 393 + 2 (–285) – (–890)] kJ mol–1 = – 73 kJ mol–1
or, equivalently, we may add the following three chemical equations.
C(graphite) + O2 (g)  CO2 (g) CH° = – 393 kJ mol–1
1
2 [H2(g) + O (g)  H2O()] rH° = 2(– 285) kJ mol–1
2 2
– [CH4(g) + 2O2 (g)  CO2 (g) + 2H2O()] rH° = –(– 890) kJ mol–1
––––––––––––––––––––––––––––––––––––––– ––––––––––––––––––––––
C(graphite) + 2H2(g)  CH4 (g) fH° = – 73 kJ mol–1
 Measurement of Enthalpy of Combustion :

Enthalpy of combustion are usually measured by
placing a known mass of the compound in a
closed steel container (known as bomb
calorimeter) which is filled with oxygen at about
30 bar pressure.
The calorimeter is surrounded by a known
mass of water. The entire apparatus is kept in an
insulated jacket to prevent heat entering into or
leaving from the container, as shown in figure.
The sample is ignited electrically to bring about
the combustion reaction. The heat evolved is used
in raising the temperature of water and the
calorimeter.
If total heat capacity of calorimeter and all of its contents = C, rise in temperature = T
then heat released = q = CT of this heat is because of mass m of substance then :
M
due to 1 mole, heat released =  m  q = EC°
 
(constant volume reaction).
Now, HC° can be calculated by using HC° = EC° + ng RT.
Where ng is the change in stoichiometric number of gaseous species in the balanced chemical equation
representing the combustion process.
Example-14 : A gas mixture of 4 litres of ethylene and methane on complete combustion at 25ºC produces
6 litres of CO2 . Find out the amount of heat evolved on burning one litre of the gas mixture. The heats
of combustion of ethylene and methane are – 1464 and –976 kJ mol-1 at 25ºC. [ IIT 1991 ]
Solution : + O2  CO2 + H2O

x lit. (4 – x)lit. 6 lit.
(say)
or x moles (4 – x) moles 6 moles
Applying POAC for C atoms,
2 × x + 1 × ( 4 – x ) = 1 × 6 ; x = 2 lit.
Thus, the volume of C2H4 = 2 lit., and volume of CH2 = 2 lit.
 volume of C2H4 in a 1 litre mixture = 2/4 = 0.5 lit.
and volume of CH4 in a 1 litre mixture = 1 –0.5 = 0.5 lit.
Now, thermochemical reactions for C2H4 and CH4 are
C2H4 + 3O2  2CO2 + 2H2O; H = – 1464 kJ
CH4 + 2O2  CO2 + 2H2O; H = – 976 kJ
As H values given are at 25ºC, let us first calculate the volume occupied by one mole of any gas at
25ºC (supposing pressure as 1atm)
298
Volume per mole at 25ºC = × 22.4 = 24.4 lit.
273
1464
Thus, heat evolved in the combustion of 0.5 lit. of C2H4 = – × 0.5 = – 30 kJ
24.4
976
and heat evolved in the combustion of 0.5 lit.of CH4 = × 0.5 = –20 kJ.
24 .4
 total heat evolved in the combustion of 1 litre of the mixture = –30 + (– 20) = – 50 kJ.
 Integral enthalpy of solution

The integral enthalpy of solution at the given concentration is the enthalpy change when one mole of
the solute is dissolved in a definite quantity of solvent to produce a solution of a desired concentration.
While recording integral enthalpies of solution it is a general practice to state the amount of the
solvent in which 1 mole of solute is dissolved ; Thus
HCl(g) + 10H2O()  HCl (10H2O) H1 = –69.5 kJ mol–1
indicates that when 1 mole of hydrogen chloride gas is dissolved in 10 mol of water, there is an
evolution of 69.5 kJ of heat. Other values are
(i) HCl(g) + 25 H2O()  HCl (25H2O) H2 = –72.3 kJ mol–1
(ii) HCl(g) + 40 H2O()  HCl (40H2O) H3 = –73.0 kJ mol–1
(iii) HCl(g) + 200 H2O()  HCl (200H2O) H4 = –74.2 kJ mol–1
(iv) HCl(g) + aq  HCl (aq) H5 = –75.0 kJ mol–1
Whenever amount of solvent is not specified then take its amount to be very large just like
in equation no. (iv).
 Enthalpy of Hydration :
Enthalpy of hydration is used in following two ways.
 Enthalpy of hydration of anhydrous or partially hydrated salts :
Enthalpy of hydration of a given anhydrous or partially hydrated salt is the enthalpy change when it combines
with the requisite amount of water to form a new hydrated stable salt.
For example, the hydration of anhydrous cupric sulphate is represented by
CuSO4(s) + 5H2O()  CuSO4.5 H2O(s)
There is a almost invariably a liberation of heat in such reactions, i.e. the value of H is negative.
CuSO4(s) + 800 H2O()  CuSO4 (800 H2O) Hr° = – 68 kJ mol–1
CuSO4.5H2O(s) + 795 H2O()  CuSO4 (800 H2O) Hr° = + 10 kJ mol–1
by subtraction, we get
CuSO4(s) + 5H2O()  CuSO4.5 H2O(s) Hr° = – 78 kJ mol–1
 Enthalpy of hydration of gaseous ions.
Enthalpy of hydration of any gaseous ion is the enthalpy change when 1 mole of the gaseous ion is hydrated
in large amount of water to form aqeous ion.
By convention, the standard enthalpy of formation of H+(aq) is taken to be zero.
Enthalpy of hydration of Cl¯ gaseous ions will be represented by :
Cl¯(g) + aq. — Cl¯(aq) Hr° = Hf° (Cl–, aq)
 Enthalpy of Neutralization :
  The amount of heat released when one gram equivalent of an acid is neutralised by one gram equivalent of a base.
or
  The amount of heat released in formation of one mole of water when an acid is neutralised by a base.
or
  Enthalpy of neutralization is defined as the enthalpy change when one mole of H+ in dilute solution combines
with one mole of OH¯ to give rise to undissociated water, i.e.
H+(aq) + OH¯(aq) — H2O() H= –57.1 kJ/mole = –13.7 kcal/mol
Remember :
  For Strong Acid + Strong Base, heat of neutralisation is always equal to –13.7 kcal/mole or –57.1 kJ/mole.
  For any other combination of acid and base this heat is less than –13.7 kcal/mole or –57.1 kJ/mole.
 Enthalpy of Ionization :
   Whenever a weak acid (or base) reacts with a strong base (or acid), the release of heat is less than 57.1 kJ mol–1.
   It is because of the fact that these acids or bases are not completely ionized in solution. Some of the heat is
consumed in ionizing there acids and bases this heat is known as enthalpy of ionization. Examples are :
HCN + Na+ OH–  Na+ + CN– + H2O rH° = – 12 kJ mol–1
CH3COOH + Na OH  Na + CH3COO + H2O rH° = – 49 kJ mol–1
+ – + –
The enthalpy of ionization can be calculated as follows. The neutralization of a weak acid, say HCN, may be
represented in two steps, namely,
Ionization HCN — H+ + CN¯ H°1 = x
+
Neutralization H + OH¯ — H2O H°2 = – 57.1 kJ/mole
The complete reaction is obtained by adding the above two steps. Thus
HCN + OH¯ — H2O + CN¯ H° = – 12 kJ/mole
Obviously, H° = H°1 + H°2
H°1 = H°H°2 = [–12 – (–57.1)] = 45.1 kJ/mole
   Greater the enthalpy of ionization of any weak acid or weak base, weaker will be the acid or base.
Example-15 : Enthalpy of neutralization of HCl by NaOH is –57.1 kJ/mol and by NH4OH is –51.1 kJ/mol. Calculate
the enthalpy of dissociation of NH4OH.
Solution : Given that, H+(aq) + NH4OH(aq) — NH4+(aq) + H2O() H = –51.1 kJ/mole
We may consider neutralization in two steps.
(i) Ionization NH4OH(aq) — NH4+(aq) + OH¯(aq) H1 = ?
(ii) Neutralization H+(aq) + OH¯(aq) — H2O() H2 = – 57.1 kJ/mole
Thus, H = H1 + H2
Therefore, H1 = H – H2 = – 51.1 kJ/mol + 57.1 kJ mol–1 = 6.0 kJ/mol
Enthalpy of Transition :
Enthalpy of transition is the enthalpy change when one mole of one allotropic form changes to another.
For example : C(graphite)  C(diamond) Htrs0 = 1.90 kJ mol–1
so if C(graphite) + O2(g)  CO2(g) HC0 = – 393.51 kJ mol-1
and C(diamond) + O2(g)  CO2(g) HC0 = – 395.41 kJ mol–1
Subtracting, we have, C(graphite)  C(diamond) Htrs0 = 1.90 kJ mol–1
Enthalpy of Precipitation :
Enthalpy of precipitation is the enthalpy change when one mole of a precipitate is formed.
For example : BaCl2(aq.) + Na2SO4(aq)  BaSO4(s) + 2NaCl(aq) rH0=–24.27 kJ mol–1
Example-16 : Calculate H° for the reaction, Ag+(aq) + Cl¯(aq)  AgCl(s) at 25°C.
Given fH°(Ag+, aq) = 105 kJ mol–1, fH°(Cl¯, aq) = –167 kJ mol–1 and fH°(AgCl, s) = –127 kJ mol–1
Solution : For the reaction Ag+(aq) + Cl¯(aq)  AgCl(s)
we have H° = fH° (AgCl, s) – fH°(Ag+, aq) – fH°(Cl¯, aq)
= [–127 – 105 – (–167 )] kJ mol–1 = –65 kJ mol–1
 Enthalpy of Formation of ions :
The enthalpy change when one mole of hydrated ions is obtained from element in its standard state as.
½ Cl2 (g) + aq  Cl– (aq) Hr° = Hf° (Cl–, aq)
By convention, the standard enthlpy of formation of H+(aq) is taken to be zero.
We have seen that H+ (aq) + OH–(aq)  H2O(l) rH0 = – 57.1 kJ mol–1
For this reaction, Hr = Hf (H2O,l) – {Hf (H , aq) + Hf (OH–,aq)}
0 0 0 + 0
Hence, at 25ºC, we get Hf0 (H+, aq) + Hf0 (OH– ,aq) = Hf0 (H2O, l) – Hr0
so Hf0 (OH– ,aq) = {– 286.1 – (– 57.1)} kJ mol–1 = – 229.00 kJ mol–1
   With the enthalpies of formation of these two ions, the enthalpy of formation of any other ion can be found
from the enthalpies of formation and solution of its pure compound with H+ or OH¯. for example, the enthalpy
of formation of Na+ can be calculated from the enthalpy of formation and enthalpy of infinite dilute solution of
NaOH. The two values are :
   The chemical equation for the formation of infinite dilute solution of NaOH(s) is
NaOH(s) + nH2O()  Na+(aq) + OH¯(aq) aqH°(NaOH, s) = –44.50 kJ mol–1
Since there are equal amounts of water on both sides of the above equation, the two enthalpies give no net
effect and thus
aqH°(NaOH, s) = fH°(Na+, aq) + fH°(OH¯, aq) – fH°(NaOH, s)
or fH° (Na+, aq) = aqH° (NaOH, s) – fH°(OH°, aq) + fH°(NaOH, s)
= [–44.50 – (–229.99) + (–425.61)] kJ mol–1 = –240.12 kJ mol–1
   Similarly, from NaCl(aq) or HCl(aq), the enthalpy of formation of Cl¯(aq) can be determined, and so on. The
changes in enthalpy of any ionic reaction can then be found from these ionic enthalpies of formation and the
usual enthalpies of formation of compounds.
Example-17 : The enthalpy of formation of H2O(l) is –285 kJ mol–1 and enthalpy of neutralization of a strong acid
and a strong base is –55 kJ mol–1. What is the enthalpy of formation of OH¯ ions ?
Solution : Given that, H+(aq) + OH¯(aq)  H2O()
fH 0 –285 kJ mol–1
neutH = fH(H2O, ) – fH(OH¯, aq)
Hence fH (OH¯, aq) = fH(H2O, ) – neutH
= [–285 – (–55 )] kJ mol–1 = –230 kJ mol–1
Example-18 : Calculate the enthalpy change when one mole of HCl(g) is dissolved in a very large amount of water
at 25°C. The change in state is : HCl(g) + aq  H+(aq) + Cl¯(aq)
Given : fH (HCl, g) = – 92 kJ mol and fH° (Cl¯, aq) = – 167 kJ mol–1
–1
Solution : For the reaction, HCl(g) + aq  H+(aq) + Cl¯(aq)

we have H° = fH°(Cl¯,aq) – fH°(HCl, g)
H° = [–167 – (–92 )] kJ mol–1 = – 75 kJ mol–1
 Bond Enthalpies :
The bond enthalpy is the average of enthalpies required to dissociate the said bond present in different
gaseous compounds into free atoms or radicals in the gaseous state. While bond dissociation enthalpy is
the enthalpy required to dissociate a given bond of some specific compound.for example the enthalpy of
dissociation of the O–H bond depends on the nature of molecular species from which the H atom is being
separated. For example, in the water molecule.
H2O(g)  H(g) + OH(g) Hr0 = 501.87 kJ mol–1
However, to break the O–H bond in the hydroxyl radical required a different quantity of heat :
OH(g)  O(g) + H(g) Hr0 = 423.38 kJ mol–1
The bond enthalpy, HH, is defined as the average of these two values, that is :
501.87mol1  423 .38kJmol1
HH = = 462.625 kJ mol–1
2
In the case of diatomic molecules, such as H2, the bond enthalpy and bond dissociation enthalpy are
identical because each refers to the reaction.
H2(g)  2H(g) HH – H = Hr0 = 435.93 kJ mol–1
Thus, the bond enthalpy given for any particular pair of atoms is the average value of the dissociation enthaplies
of the bond for a number of molecules in which the pair of atoms appears.
 Estimation of Enthalpy of a reaction from bond Enthalpies :

Let the enthalpy change for the gaseous reaction
be required from the bond enthalpy data. This may be calculated as follows :
 Enthalpy required to break reactants    Enthalpy released to form products 
H =  into gasesous atoms   from the gasesous atoms 
   
= [4HC–H + HC=C + HH–Cl]R + [–5HC–H – HC–C – HC–Cl]P
= (HC=C + HH–Cl) – (HC–H + HC–C + HC–Cl)
Example-19 : Using the bond enthalpy data given below, calculate the enthalpy change for the reaction
C2H4(g) + H2(g)  C2H6(g)
Data : Bond Bond enthalpy
C–C 336 kJ mol–1
C=C 606 kJ mol–1
C–H 410 kJ mol–1
H–H 431 kJ mol–1
Solution : Diagrammatically, we represent the given reaction as follows :
H H H H
| |
C=C (g) + H H(g) H H C C H
| |
H H H H
Break Break make bond
bonds bonds
H H
2C(g) + 4H(g) + 2H(g) H C C H
H H
Hr = (4HC–H +HC=C + HH–H) – (6HC–H +HC–C)

= (4 × 410 + 606 + 431) – ( 6× 410 + 336)
= 2677 – 2796
= – 119 kJ/mol.
Example-20 : Using the bond enthalpy data given below, estimate the enthalpy of formation of gaseous isoprene
CH2  C  CH  CH2
|
CH3
Data Bond enthalpy of C – H bond = 413.38 kJ mol–1
Bond enthalpy of C – C bond = 347.69 kJ mol–1
Bond enthalpy of C = C bond = 615.05 kJ mol–1
Enthalpy of sublimation of carbon (graphite) = 718.39 kJ mol–1
Enthalpy of dissociation of H2(g) = 435.97 kJ mol–1
Solution : For isoprene, we have to form
2C – C bonds ; 2C = C bonds and 8C – H bonds
Method-1 For which energy released is
[2(+347.69) + 2(+615.05) + 8(+413.38)] kJ mol–1 = 5 232.52 kJ mol–1
that is, H (from gaseous atoms) = + 5232.52 kJ mol–1
The reaction corresponding to this is
5C(g) + 8H(g)  C5H8(g) fH1 = – 5232.52 kJ mol–1
But we want fH corresponding to the following equation
5C(graphite) + 4H2(g)  C5H8(g) fH = ?
This can be obtained by the following manipulations :
5C(g) + 8H(g) C5H8(g) rH2 = – 5232.52 kJ mol–1
5C(graphite)  5C(g) rH3 = 5 × 718.39 kJ mol–1
4H2(g)  8H(g) rH4 = 4 × 435.97 kJ mol–1
Adding, we get
5C(graphite) + 4H2(g)  C5H8(g) fH = 103.31 kJ mol–1
Method-2 Diagrammatically, the above calculations may be represented as follows.
Applying Hess’s law, we get

fH = 5H3 + 4H4 – 2HC = C – 2HC – C – 8HC – H
= (5 x 718.39 + 4 x 435.97 – 2 x 615.05 – 2 x 347.69 – 8 x 413.38) kJ mol–1
fH = 103.31 kJ mol–1
Example-21 : Find the bond enthalpy of S – S bond from the following data :
C2H5 – S – C2H5(g) fH° = – 147 kJ mol–1
C2H5 – S – S – C2H5(g) fH° = –201 kJ mol–1
S(g) fH° = 222 kJ mol–1
Solution : Given that
Method-1 (i) 4C(s) + 5H2(g) + S(s)  C2H5 – S – C2H5(g) fH° = –147 kJ mol–1
(ii) 4C(s) + 5H2(g) + 2S(s)  C2H5 – S – S – C2H5(g) fH° = –201 kJ mol–1
Subtracting Eq. (i) from Eq. (ii), we get
C2H5 – S – C2H5(g) + S(s)  C2H5 – S – S – C2H5(g) rH° = –54 kJ mol–1
Adding to this, the following equation
S(g)  S(s) fH° = –222 kJ mol–1
We get
C2H5 – S – C2H5(g) + S(g)  C2H5 – S – S – C2H5(g) rH° = –276 kJ mol–1
In the last equation 276 kJ of heat evolved because of the S–S bond formation.
Hence, the bond enthalpy of S – S is 276 kJ mol–1.
Method-2 Diagrammatically, we may represent the above calculation as follows :
According to Hess’s law
rH° = Enthalpy involved in bond breaking vap Hº(s) – Enthalpy involved in bond making
rH° = [2HC – C + 10HC–H + 2HC–S + vap H(S)] + [–2HC–C – 10HC–H – 2HC–S – HS–S]
= vapH°(S) – HS–S
or HS–S = vapH°(S) – H°
= vapH°(S) – [fH°(C2H5 – S – S – C2H5] – fH°(C2H5 – S – C2H5)]
= [222 – {–201 – (–174)}] kJ mol–1 = 276 kJ mol–1
 Resonance Energy :
Difference between energy of resonance hybrid and resonating structure in which resonance hybrid have
lower energy because stabilised by resonance.
H°resonance = H°f, experimental – H°f, calclulated
= H°combustion, calclulated– H°combustion, experimental
Example-22 : Calculate the heat of formation of benzene from the following data, assuming no resonance. Bond
energies :
C – C = 83 kcal, C C = 140 kcal, C – H = 99 kcal
Heat of atomisation of C = 170 .9 kcal
Heat of atomisation of H = 52.1 kcal
Solution : We have to calculate H for the reaction
6C (s) + 3H2(g)  C6 H6 (g)
For reactants :
Heat of atomisation of 6 moles of C = 6 ×170.9 kcal
heat of atomisation of 6 moles of H = 6 × 52.1 kcal
For products :
Heat of formation of 6 moles of C – H bonds = – 6 × 99
Heat of formation of 3 moles of C–C = – 3 × 83
Heat of formation of 3 moles of C C bonds = –3 × 140
on adding, we get heat of formation of C6H6,i.e.,
fH = 6 ×170.9 + 6 × 52.1– 6 × 99 – 3 × 83 –3 × 140 = –75 kcal
MISCELLANEOUS SOLVED EXAMPLES

1. Find (in terms of "a") the amount of energy required to raise the temperature of a substance from 3 K
to 5 K . At low temperatures. CP = aT 3 .
3
Sol. q=  nC p ·dT =  naT · dT
5
 T4  na
= na  4  = [(5)4 – (3)4]
  4
3
na 625 – 81
= = 136 na. Ans. q = 136 na.
4
2. A thermally isolated vessel contains 100 g of water at 0°C. When air above the water is pumped out, some
of the water freezes and some evaporates at 0°C itself. Calculate the mass of the ice formed such that no
water is left in the vessel. Latent heat of vaporization of water at 0°C = 2.10 x 106 J/kg and latent heat of fusion
of ice = 3.36 x 105 J/kg.
Sol. Total mass of the water = M = 100 g
Latent heat of vaporization of water at 0°C
= L1 = 21.0 x 105 J/Kg
& Latent heat of fusion of ice = L2 = 3.36 x 105 J/Kg
Suppose, the mass of the ice formed = m
Then, the mass of water evaporated = M – m.
Heat lost by the water in freezing = Heat taken by water in evaporation.
Thus, mL2 = (M – m) L1 or m = 86 g. Ans. 86.2 g
3. Work done in expansion of an ideal gas from 4 litre to 6 litre against a constant external pressure of 2.1
atm was used to heat up 1 mole of water at 293 K. If specific heat of water is 4.2 J g –1 K–1, what is the
final temperature of water ?
Sol. W = – 2.1 [6 – 4] = – 2.1 × 2
= – 4.2 atm × lit.
= – 4.2 × 101. 325 J
This work is used to heat up the water
J
Specific heat of H2O = 4.2 gram ·K.
Heat required for increasing temperature by 1°C of 1 mole = 4.2 × 18 = 75.6 J
4.2 × 101.325 = 75.6 [T – 293]
5.63 = T – 293
T = 298.63 K Ans. 298.63 K
4. 1 mole of ice at 0°C and 4.6 mm Hg pressure is converted to water vapour at a constant temperature and
pressure. Find H and E if the latent heat of fusion of ice is 80 cal/g and latent heat of vaporisation of liquid
water at 0°C is 596 cal/g and the volume of ice in comparison to that of water (vapour) is neglected.
Sol. No. of mole = 1 mole
T = 273 K.
Pv = nRT.
4.6
v = 1 × 0.0821 × 273
760
v = 3699 lit [3700 lit]
latent heat of fusion = 80 cal/gram Latent heat of vaporisation = 596 cal/gram
H = 80 × 18 + 596 × 18 = [80 + 596] × 18
H = 12168 cal
H = E + P [V2 – V1]
4. 6
12168 = E + [3699] × 24.24
760
4.6
 E = 12168 – × 3699 × 24.24
760
= 12168 – 542.72 = 11625.28 cal. Ans. 12168 cal, 11625.28 cal
5. For Ag, CP (JK–1 mol–1) is given by 24 + 0.006 T. Calculate H if 3 mol of silver are raised from 27°C to its
s
melting point 927°C under 1 atm pressure.
T2 T2
1
Sol. H   nCp dT   3(24  .006T)dT = 3 [ 24 (T2–T1) + × 0.006 ( T22  T12 )]
T1 T1
2
= 3 × 25650 = 76950 J Ans. 76950 J
6. Calculate the amount of heat evolved during the complete combustion of 100 ml of liquid benzene from the
following data.
(i) 18 g of graphite on complete combustion evolve 590 KJ heat
(ii) 15889 KJ heat is required to dissociate all the molecules of 1 litre water into H2 and O2.
(iii) The heat of formation of liquid benzene is 50 kJ/mol
(iv) Density of C6H6 () = 0.87 g/m
Sol. (i) C(s) + O2(g)  CO2(g) ; H ºf = – 393.33 KJ/mol
1
(ii) H2(g) + O (g)  H2O () ; H ºf = – 286 KJ/mol
2 2
15
(iii) C6H6() + O (g)  6CO2 (g) + 3H2O ()
2 2
 Hº = [6(–393.33) + 3 (–286)] – 50 = –3268 KJ/mole
 Heat evolved from 87 g benzene = 3645 KJ Ans. 3645 KJ
7. For the equations C(diamond) + 2H2(g)  CH4(g) H1 ; C(g) + 4H(g)  CH4(g) H2
Predict whether
(A) H1 = H2 (B) H1 > H2
(C) H1 < H2 (D) H1 = H2 + vapH(C) + dissH(H2)
Ans. (B)
8. The standard molar enthalpies of formation of cyclohexane (l) and benzene (l) at 25º C are -156 and + 49 KJ
mol–1 respectively. The standard enthalpy of hydrogenation of cyclohexene (l) at 25º is –119 kJ mol–1. Use
these data to estimate the magnitude of the resonance energy of benzene.
Sol. Enthalpy of formation of 3 carbon-carbon double bonds
= HF ( ) –  Hf ( )
= –156 – (+ 49) kJ = –205 kJ.
Given that, + H2  H = 119 kJ
Theoretical enthalpy of formation of 3 double bonds in benzene ring
= 3 × (–119) kJ = – 357 kJ.
 resonance energy of benzene = – 357 – (–205) kJ = –152 kJ mole–1 Ans. –152 kJ mole–1
9. Following graph shows a single stange expansion process, then workdone P(atm)
by the system is
(A) – 9104 J 5
(B) – 202.6 J
1
(C) – 506 J
(D) – 101.3 J 2 4 V(ltr)
Sol. 1 Ans. (B)
V (Lit)
0 2 4
W = – Pext (V2 – V1) = – 1 × 2 × 101.325 J = – 202.6 J

10. A sample of 2 kg of helium (assumed ideal) is taken through the process
ABC and another sample of 2 kg of the same gas is taken through the
B C
process ADC. Then the temperature of the states A and B are (Given R = 10
P(10 N/m )
2
8.3 joules/mol K) :
4
(A) TA = 120.5 K, TB = 120. 5K (B) TA = 241 K, TB = 241 K

5 A D
(C) TA = 120.5 K, TB = 241 K (D) TA = 241 K, TB = 482 K
10 20V(m3)
5 2  1000
0.5  10
Sol. × 10 × 103 = × 0.082 TA
1.01 105 2
1
= 0.082 TA
1.01
TA = 120.5 K
at constant volume
PA PB

TA TB
PB .TA 10
TB = PA = 5 × 120.5 = 241 K. Ans. (C)
11. In an isothermal expansion of a gaseous sample the correct relation is (consider w (work) with sign according
to new IUPAC convention)
[The reversible and irreversible processes are carried out between same initial and final states.]
(A) wrev > wirrev (B) wirrev > wrev (C) qrev < qirrev (D) can not be predicted
Ans. (B)
12. One mole of an ideal monoatomic gas is caused to go through the cycle
2P0 c
shown in figure. Then, the change in the internal energy in expanding the
gas from a to c along the path abc is :
Pressure
T0
(A) 3 P0V0 (B) 6 RT0 P0 b
a
(C) 4.5 RT0 (D) 10.5 RT0

V0 4V0
Volume
Sol. Pv = nRT at point C
2P0 × 4v 0 = 1 × RTC
 8P0 V0 
TC =  
 R  C
Pressure
2P0
at point a
P0V0 = 1 × RT0 T0
P0 V0 P0
a b
T0 = ; T C = 8 T0
R
Change in internal energy = [nCVdT]
v0 4v0
3 9 Volume
For path a to b = 1 × R × [3T0] = RT0
2 2
3
For path b to c = 1 × R × [4T0] = 6T0 R
2
9 21RT0
Total change = RT
T0 + 6RT0 = = 10.5 RT
T0 .
2 2
So total change in internal energy
U = 10.5 RT0 Ans. (D)
13. A certain mass of gas is expanded from (1L, 10 atm) to (4L, 5 atm) against a constant external pressure of
1 atm. If initial temperature of gas is 300 K and the heat capacity of process is 50 J/°C. Then the enthalpy
change during the process is (1L atm ~ 100 J)
(A) H = 15 kJ (B) H = 15.7 kJ (C) H = 14.4 kJ (D) H = 14.7 kJ
Sol. H = E + (PV) & E = q + W = (50 × 300 – 3 ×100) J [as Tf = 2 × 300 K = 600 K] = 14.7 kJ
H = 14700 + 10 × 100 = 15700 J = 15.7 kJ. Ans (B)
14. One mole of an ideal monoatomic gas expands isothermally against constant external pressure of 1
atm from initial volume of 1L to a state where its final pressure becomes equal to external pressure. If
initial temperature of gas is 300 K then total entropy change of system in the above process is :
[R = 0.082 L atm mol –1 K–1 = 8.3 J mol –1K–1].
(A) 0 (B) Rn (24.6) (C) R n (2490) (D) 3/2 Rn (24.6)
Vf   Pi   300R 
Sol. S = nR n  V  = Rn 
P

 = R n  1 L  1 atm  = Rn (24.6) Ans. (B)
 i  f   
15. For a perfectly crystalline solid Cp.m. = aT3, where a is constant. If Cp.m. is 0.42 J/K–mol at 10 K, molar entropy
at 10 K is :
(A) 0.42 J/K-mol (B) 0.14 J/K-mol (C) 4.2 J/K-mol (D) zero
Sol. 0.42 = a(10)3  a = 0.42 × 10–3
10 10
Cp.m. 2 a 0.42
Sm =  dT =  aT  [10 3  0]   0.14 J / K  mol Ans. (B)
0
T 0
3 3
16. Given the following data :

Substance H° (kJ/mol) S°(J/mol K) G° (kJ/mol)
FeO(s) – 266.3 57.49 – 245.12
C (Graphite) 0 5.74 0
Fe(s) 0 27.28 0
CO(g) – 110.5 197.6 – 137.15
Determine at what temperature the following reaction is spontaneous ?
FeO(s) + C (Graphite)  Fe(s) + CO(g)
(A) 298 K (B) 668 K (C) 966 K
(D) G° is +ve, hence the reaction will never be spontaneous
Sol. FeO (s) + C (graphite)  Fe (s) + CO (g)
(1) H = 0 + [– 110.5] – (– 266.3)
= –110.5 + 266.3
= + 155.8 kJ/mole
(2) S = 27.28 + 197.6 – 57.49 – 5.74 = 161.65 J/mole
(3) G = H – TS = 0 = 155.8 – T × 161.65 × 10–3
T × 161.65 × 10–3 = 155.8  T = 963.8 K Ans. (C)
17. If Hfº for Ag+ (infinitely diluted), NO3¯ (infinitely diluted), Cl¯ (infinitely diluted) and AgCl(s) are 105.579,
–207.36, –167.159 and –127.068 respectively. Calculate the enthalpy change for the reaction
AgNO3(aq.) + HCl(aq.)  AgCl(s) + HNO3 (aq.)
(A) 21.471 KJ/mol (B) 145.688 KJ/mol (C) –65.488 KJ/mol (D) None
Sol. Hºreaction = [Hf (AgCl) + Hf (H+) + Hf(NO3¯)]
– [Hºf (Ag+)] + Hºf (NO3¯) + Hºf (Cl¯) + Hºf (H+)]
= – 127.068 – [105.579 –167.159] = – 65.488 KJ / mol. Ans. (C)
18. What is the work done against the atmosphere when 25 grams of water vaporizes at 373 K against a
constant external pressure of 1 atm ? Assume that steam obeys perfect gas laws. Given that the molar
enthalpy of vaporization is 9.72 kcal/mole, what is the change of internal energy in the above process ?
(A) 1294.0 cal, 11247 cal (B) 921.4 cal, 11074 cal
(C) 1025.6 cal ; 12474.3 cal (D) 1129.3 cal, 10207 cal
Sol. Mole of H2O = 1.39
Pv = nRT
1 × v = 1.39 × 0.082 × 373
v = 42.51 lit
42.80  101 .325
w = Pext. dv = 1 × [42.80] atm × lit. = 42.80 × 101.325 J = = 1025.6 cal
4.2
H = U + [Pv]. = 12470.6 cal. Ans. (C)
U = H – Pv = 13500–1025.6 =12474.3 cal

(5285) Sheet Thermodynamics and Thermochemistry TH e

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Thermodynamics & Thermochemistry

Example-1 : A+B C+ D K1, eq = 103

Terms to be used in Thermodynamics :

Ex. Air in a room, water in a bottle, any living body.

 Surrounding : Rest of the universe.

 Boundary : Anything which separates system & surroundings is called boundary.

Open System Close System Isolated system

How to identify extensive or intensive properties

(b) Thermal equilibrium

 Thermal equilibrium : There should not be any temperature gradient (difference).

For piston to be in equilibrium : Pgas = Patm + Mg/A

Now, there are two ways in which system can be chosen.

–System : All contents of the container (water + Heater coil).

 IUPAC Sign convention about Heat and Work

IUPAC convention of Heat

Zeroth Law of Thermodynamics (ZLOT) :

First Law of Thermodynamics (FLOT) :

 Calculation of different quantities in First Law of Thermodynamics (FLOT) :

 Molar heat capacity (C)

For isothermal process C =±  For isobaric process C = Cp

WORK DONE (w) :

 Calculation of work for different type of process on an ideal gas.

Work = Area under the P–V diagram

(iii) For n step expansion and n  

Patm (Patm + M0g/A) = Pf

(ii) Two step compression :

If m1 is placed first, then the first compression

 If expansion/compression takes place against constant external pressure then it is irreversible.

Reversible and irreversible isothermal process. A

 Except the infinite stage compression/expansion, all are irreversible.

1 litre atm = 101.3 J

Note :- At high temperature vibrational degree of freedom is also included.

(b) Irreversible Adiabatic

 Comparison of single stage Vs two stage expansion(adiabatic).

nR(T2  T1 ) P2 V2  P1V1 P1V1 P2 V2

Case - II For solids and liquid system :

Case - III For chemical reactions :

 W = – Pext. [VC’(g) – VC(g)]

Case - IV During phase transformation.

S.No. Process w q U H Molar heat capacity

2. Isobaric Pext  V2  V1  nCp,m  Tf  Ti  q + w nCp,m  Tf  Ti  Cp,m

 IInd Law of thermodynamics :

As ‘S’ is a state function. Hence ’S’ will also be a state function.

 Entropy calculation for an ideal gas undergo in a process.

from the first law

for an ideal gas

As irreversible work of gas is more than reversible work.

Suniverse = Ssys + Ssurrounding = 0

Suniverse = Ssys + Ssurrounding = 0

 Entropy Calculation for phase transformations

(b) Two copper block kept in contact in thermostat

 Third Law Of Thermodynamics :

 For chemical reaction

 For phase transformations

Greaction = G°reaction + RTlnQ

Gibb’s Helmholtz Equation :

Suniverse = Ssystem + Ssurrounding

= heat added at constant pressure to change temperature from 25°C to 50°C.