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CHEMISTRY LECTURE NOTES

COURSE - VIKAAS (A)


(LECTURE No. 1 TO 13)

TOPIC : THERMODYNAMICS

PAGE _ 1
LECTURE#1

THERMODYNAMICS

First law of Thermochemistry Second law of


Thermodynamics (application of I law in Thermodynamics
chemical reactions)

Thermodynamics : The branch of science which deals with different forms of energy & their interconversion.
In chemistry using Thermodynamics.
(a) We can predict that if two substances are mixed then the reaction between them will takes place or
not.(feasibility of the reaction)
(b) If Reaction does take place then what are the energy changes involved during the reaction.
(c) 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 :
(1) 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).
(2) Using thermodynamics we cannot calculate the time taken for completion of a reaction or for attainment of
chemical equilibrium.

Q.1 A+B C+ D K1, eq = 103


E+F G+H K2, eq = 103
Which of these reaction will attain equilibrium earlier ?
Ans. 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 :
(1) System, surroundings and boundary.
(a) System : A specified part of the universe selected for the study of effect of certain properties such as P,T
etc.

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


(b) Surrounding : Rest of the universe.
System + Surroundings = universe.
(c) Boundary : Anything which separates system & surroundings is called boundary.
Boundary can be real or imaginary.
Boundary can be flexible or rigid(for example - air in a flexible balloon(flexible boundary) while air in a room
(fixed boundary).
Boundary can be adiabatic(non-conducting) or diathermic(conducting).
(d) Types of system :
(1) Open system : System which can exchange energy & matter both with the surroundings.
Ex. Living systems( any living organism) are open systems, air in an open room.
(2) Closed system : System which can exchange only energy but cannot exchange matter with the surrounding
is called closed system.
Ex. any matter in a closed container.

PAGE _ 2
(3) Isolated system : System which cannot exchange energy and matter both with the surroundings.
Ex. (1) 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).
(2) Whole of universe is a perfect isolated system.
Q. Human body is an example of :
(A*) open system (B) closed system (C) isolated system (D) none of thse
Sol. Human body can exchange energy & matter with surroundings. This represents open system.

(2) State of a system :


It means the condition in which the system is present and it can be specified/defined by measuring/ specifying
some observable/measurable properties of the system.
Ex. For an ideal gaseous system state of the system can be defined by specifying volume, temperature and
pressure.
For other systems we may have to specify more properties of the system depending on the complexity of the
system.
(3) State functions & path functions :
State function : Any property of the system which is dependent only on the state of the system and not on
the way that state has been achieved.
Ex. ( 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.
Ex.

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.
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.).
State functions have a fixed value (measurable or unmeasurable) in a particular state of the system while the
path functions have values or are defined only when there is some process or when system changes its
state from one thermodynamic equilibrium state to another, these can not have any particular value in any
particular state of the system.
(4) Extensic & intensive functions :
Extensive functions : Functions or properties of the system which are dependent on mass or on size of the
system.
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. While the volume 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.

PAGE _ 3
Ex. Volume, Mass, Total heat capacity, Total internal energy (E), Enthalpy(H), Gibbs Free
Energy(G), Entropy(S).

Extensive functions are additive in nature( The addition of the volumes of the two parts equals the volume of
the whole of the room.)
Intensive functions : Functions or properties which are not mass dependent or size dependent are called
intensive function.
Ex. Temperature, pressure, molar heat capacity, specific heat capacity, density,concentration, vapour pressure.
Intensive properties are not additive in nature.
(5) 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
(a) 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.

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

Temperature may have different values at different places/locations in a system but it should remain constant
with time
(c) Chemical equilibrium : There should not be any concentration gradient of any of the species in the
system.
(6) 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
dT = 0
T = 0
2. Isochoric process : V = constant
dV = 0
V = 0
3. Isobaric process : P = constant
dP = 0
P = 0
4. Adiabatic process : q=0
or heat exchange with the surrounding = 0(zero)

PAGE _ 4
LECTURE#2
Classification of thermodynamics processes on the basis of the way these processes are carried out:
1. Reversible process
2. Irreversible process/spontaneous process/Natural process.
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.
OR
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 dF and dF 0
An ideal reversible process will take infinite time to get completed.
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

Irreversible process : If a process is carried out in such a manner so that the system is in thermodynamic
equilibrium only at initial & final state of the process but not at the intermediate stages.(or system should be
in thermodynamic equilibrium state at some finite number of intermediate stages only - for example - n step
irreversible expansion of a gas)
OR
If during the process there is a finite difference in driving force and opposing force so that process takes place
with a finite rate.

Irreversible processes will get completed in finite time.


In case of any irreversible process at intermediate stages of the process the different state function such as
Pressure, temperature etc. are not defined. 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.

PAGE _ 5
(7) Heat & work : These are two ways by which a system can interact or can exchange energy with its
surroundings.
Heat & work both are forms of energy.

Heat : When the energy transfer both system & surroundings takes place because of temperature difference.

Work : Any energy transfer which is not heat or which is not because of temperature difference is called
work.Work can be of many types such as 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 25C,
the surroundings is also at temperature of 25C 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 25C 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.

1. IUPAC Sign convention about Heat and Work


Any energy given to system is taken positive so heat given to system = positive
heat given out from system / 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. Do not get panicked - take it lightly it is not a big
difference. You can easily absorb it.
So if in any problem, w = 103
It means system has done work of 10 J on surroundings.
1st Law of Thermodynamics

Law of energy conservation : -Energy of total universe is always conserved.


oR
Total energy of an isolated system is always conserved.
OR
To develop a mathematical expression for 1st Law of thermodynamics first we have to define a from called
total internal energy of system (E or U symbol)
E - summation of all type of energies.
E = Translational KE + Rotational KE + Vibrational KE + electrostatic PE + nuclear PE + bonding energy
+ ............................ (energy term of undiscovered forces)
Hence absolute value of E can never be calculated only change in value of E can be calculated for a particular
process.

PAGE _ 6
Mathematical form of 1st Law of thermodynamics.
If a system is intially 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

Q. A system does 100 J work on surroundings by absorbing 150 J of heat. Calculate the change in internal
energy.
Sol. w = 100 J, q = 150 J
So, E = q + w = 150 100 = 50 J

Calculation of different quantities in equation of 1st Law of thermodynamics.

E = Calculation for an ideal gas.

For an ideal gas E is a function of temperature only - Also known as Thermodynamic definition of an ideal
gas
E E
so =0, =0
V T P T
Further, with change in temperature only the kinetic energy get change, not any of the potential energy, So
E = (Translational KE) + (Rotational KE)
+ (Vibrational KE) + 0 + 0 + 0 .....................
1
Now according to law of equipartition of energy, each degree of freedom contributes RT (per mole)
2
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.

Law of equipartition of energy :


1
* Energy equal to KT is associated with each degree of freedom per ideal gas molecule
2

1
U/molecule = f x KT
2

f
U/mole = x KT NA
2

f
U/mole = RT
2

f
For n moles = nRT
2

f
U= nRT only for ideal gas.
2

Vibrational energy changes for Law Temperature increments can be neglected.


so E = (Tranlational KE) + (Rotational KE)
3 fR
= RT + nRT
2 2

f
= nR (T)
2

PAGE _ 7
f
E = nR (T)
2
where of - initial degrees of freedom for that gas.
f=3 for monoatomic
=5 for diatomic or linear polyatmic
=6 for non - linear polyatmic

Calculation of heat (q)

heat is a path function and is generally calculated indirectly using Ist law of thermodynamics first
of all calculate E and W & then q. Heat can be caluclated if heat capacity of any process is given
to us.
Heat capacity is a path function and different type of heat capacities are defined [Remember heat capacity
of a substance is not fixed it is dependent on type of process which is being performed on that substance]
Total heat capacity Heat required to raise the temperature of system by 1C under the given process.
q dq
CT = = J/C
T dT
It will be extensive path function
So dq = cdT

&q= cdT
Molar heat capacity heat required to raise temperature of 1 mole of a subtance by 1C
q dq
C= = J mole1 K1
nT ndT
So. dq = ncdT

q= ncdT ncT
for an ideal gas CP and CV are very much used.
Specific heat capacity (s) : heat required to raise temperature of unit mass (generally 1 gm) of a substance
by 1C.
q dq
S= = Jgm1 K1
m T mdT
so dq = msdT

q= dq ms dT msT
We can define specific heat capacity at constant pressure and at constant volume.(sP & sV )
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 mass 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

Q. 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/C final E of gas if the final temperature of gas is 25C higher than its initial temperature.
Sol. T = 25
w = 100 , q = CT = 2 25 = 50
E = q + w = 50 + (100) = 50 J

Note: Hence we can see that heat capacity (C) is a path function, but remember Cp and CV are not path
functions these are constants.
Heat capacity can have volue from to + as depending on process.

PAGE _ 8
LECTURE#3
WORK DONE (w) :
Energy that is transmitted from one system to another in such a way that difference of temperature is
not directly involved. This definition is consistent with our understanding of work as dw = Fdx. The
force F can arise from electrical, magnetic, gravitational & other sources . It is a path function .
Note : You will frequently encounter (litre. atmosphere) term which has units of energy . It is useful to remember
the conversion : 1 litre. atm = 101.3 Joules = 24.206 cal
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. Hence it is also used
sometimes.
For irreversible processes, state parameters such as P,T etc cannot be defined. Hence work cannot
be estimated using Pgas. 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 ext = Pext .dv



Work : dW = Fext dx
P-V Work :
Assuming that under an external force Fx, the piston moves down by a distance dx.

Fext
dx

Fext
dW ( A dx ) dW = Pext (dV)
A
As the work done in the above case by the external agent is +ve and as the expression conveys otherwise,
hence a -ve sign is introduced.
dW = Pext. dV

Q. A gas abosrbs 200 J of heat and expands against the external pressure of 1.5 atim from a volume of 0.5 Lt
to 1.0 Lt. Calculate the change in internal energy.
Sol. w = PV = 1.5 (10.5) = 0.75 Lt atm.
= 0.75 101.3 J = 75.975 J
Now E = 200 75.975 = 124.025 J.

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


(a) Isothermal Reversible expansion of an ideal gas.
Let initial pressure of gas be Pi and initial mass of sand
placed to keep equilibrium be m0, so
m0g
pi = patm +
A
A = Area of cross section of pistion

PAGE _ 9
Now af some intermediate stage of expansion let the volume has become V and mass of remaining sand be
m, then as process is reversible, so there is equailibrium (always). so
mg
pext = patm + = pgas = p
A
nRT
As process is isothermal so P =
V
where n is mo. of moles of gas enclosed and T = temperature of gas = temp. of constant temp. both
Now if volume of system is increased by dv amount by displacing a small mass of sand from above the pison
so
Pext Pgas = dp 0
then work done in this slight expansion
dw = Pext. dv = = Pgas . dv (with IUPAC sing conversion)
To obtain the total work done. We have to do the integration so
Vf Vf Vf Vf
nRT
W= dw Pext dv =
Pgas dv = P dv so W = . dv
V
Vi Vi Vi Vi

W = nRT ln (Vf/Vi)

Pi

Pressure dw
P
P dp)

This process can also be repressnted in a PV digram as follows


Patm = Pf

Vi V(v+dv) Vf

Here we have assumed pf = Patm need not become for a given problem
Total work done is area under the pv diagram only in case of reversible process the pressure of gas at
intemediate stages is difined and hence the process can be repressnted in pv diagram

(b) Irreversible isothermal expansion of a gas

There are many ways in which a gas can be expanded inersible and siothermally.
(i) Single step irrersible isothermal expansion
here 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 initally to maintain equilibrium jnitially
Pi Pgas Patm + mog/A

for expanstion to take place, m0 mass is snddenly removed so gas expands against constant external
pressure of Patm

PAGE _ 10
In this case the pressure of gas will not be defined as the sndden expansion has taken place so all the
molecules of sampel will not get the infamation of expansion simultaneasly, there will be a time gap and
hence there will be a state of turbulence.
But just below the piston the pressure of gas will be equal to external pressure, Patm (using work energy
thearm, or total force on a massless piston must be zero)
so from some intemediate state of volume v the work done is slight expansion from
V (V + dv)
dw = Pext . dv (IUPAC sign conrention)
Vf

so W= dw Pext .dv

Vi

W = Pext (Vf Vi)

PV digram Repressentation

Only initial and final states can be located (as at intemediate stages pressure of gas is not defined)
work done by gas is less in this case in comparision to work done during reversible expansion

(ii) Two step imersible isothermal expansion of mass m0 is divide into hw mass (may be equal or
unequal)
M0 (m1 m 2 )
Now if m1 only is removed than the expansion of gas will take place against constant extermal pressure
Pext = (Patm + M2g/A)
and this expansion will take place only upto expansion will take place only upto volume V1 such that
Pext. V1 = Pi Vi (isothermal)
Now if second mass m2 is also removed then expansion
Vi Vf will take place against constant pressure
Pext = Patm
So

Patm

M1
Vf M0
V
work done is expansion Vi V1 Vi

W 1 = (Patm +M2g/A) (Vi V1)

& work done is expansion V1 Vf

W 2 = Patm (Vf Vi)

Toral work = W 1 + W 2

PAGE _ 11
Pi

Patm + M 2g/A)
(

PV Diagram representation
Patm W1
W2
Vi V1 Vf
Volume

Note that m1 & m2 are symbolic only there need not be actual m1 & m2 just have to do expansions in hw
steps.
Again note that work done is this ineresible expansion is smaller than work done by gas during the rerersible
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.

Pi

Pressure

(iii) for n step expansion n

Vi Volume Vf

In the limit n . This irrevesible process will become reversible one

Conclusion :
Whenever system/gas does work on. surroundings it will be maximum in case of reversible process.
(c) Reversible isothermal compression of an ideal gas
This can be achieved by placing particules of equal 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 exacthy 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 + M0g/A) = Pf
Patm

Vi
Vi Patm

Vf Vi

PAGE _ 12
(d) Irreresible isothermal compression of an ideal gas

(i) single step compression :


To compress gas irrersible 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= dne V i
Pext. dv

W = Pext = (Vf Vi)

Pext

Pressure
Vf Volume Vi

(ii) Two step compression :


Place mass m0 in hw fragments (m1 + m2) the graphical representation will make the colmlation of work done
clear
Pressure

W2 W1

Patm = Pext

Vf Volume Vi

If m 1 is placed first then the first compression has taken taken place aganist external pressure of
(Patm + m2g/A)
so W 1 = (Patm + M1g/A) (V1 Vi)
Simlarly, W 2 = (Patm + M0g/A) (Vf Vi)
and n step compression in the limit n 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 designd 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 sumoundings

Wherever expanstion/compression takes place against constant external pressure then the process is
reversible.

PAGE _ 13
Q.3 Calculate the work performed when 2 moles of hydrogen expand isothermally and reversibly at
25C form 15 to 50 litres.
Sol. We have,
V2 50
W = 2.303 n RT log V = 2.303 2 2 298 log = 1436 calories.
1 15

Q.4 If a gas at a pressure of 10 atm at 300 k expands against a constant external pressure expands against a
constant external pressure of 2 atm from a vol. of 10 litres to 20 litres find work done ? [Isothermal process]
Sol Process is irreversible
20
w 2dv [20 10] = 20 J.

10

1 litre atm = 101.3 J

(e) Reversible and irreversible isochoric processes.

Since dV = 0

So dW = Pext . dV
= 0.

(f) Reversible isobaric process :

Isobaric, Pgas = constant

Since pressure of gas is defined during whole of the process and hence the process must be reversible

So due = Pext dV
= Pgas dV
Vf
= V dV W = P (Vf Vi)
i

PAGE _ 14
LECTURE#4
(g) Adiabatic reversible expansion

dQ = 0 (no heat changed b/w) system and sorrods


du = dQ + dW
nCV dT = PdV
nRT
nc V dT V
. dv

T2 V2
C v .dT R
T = V . dT
T1 V1

T2 V2
Cv ln T = P ln V
1 1

R / c v
T2 V2
ln T = ln
1 V1

1
T2 V1

T1 V2
T2 V2 1 = T1 V1 1
or T V1 = constant
PV = constant
This is only valid when
The quantity Pv or Tv 1 is contant only for a quasi static or reversible process.
For inreversible adeabatic process these equations are not applicable

Operation of adiabatic process


(a) Reversible Adiabatic

PAGE _ 15
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 contant pressure and no of moles, V T
K
w= Pext. dv but Pext = Pint =
VY

K
w= V Y . dv
K V2 1 V1 1 / 1

as K = P2V2 = P1V1

1
P2 V2 .V2 P1V1 .V11
=
1

P2 V2 P1V1
= work done
1
(b) Irreversible Adiabatic
(h) Adiabatic irreversible expansion

W= P
ext.dv

= Pext (V2 V1)

or du dw
w = u
w = nCv (T2 T1)
nR(T2 T1 ) P2 V2 P1V1 )
= =
1 1

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. In other words if
two states A and B are connected by a reversible path then they can neven be connected by an irreversible
path. There lies only one unique adiabatic path linkage between two states A and B.

PAGE _ 16
Adiabatic Expansion using single stage & Infinite stage

P2 V2 T2 P2 V2 T2

reversible single stage


wgas (reversible process
wg as )10v
P1 V1 T1 P1,V1, T1

(W gas)rev > (W gas)irrev ,urev. > uirrev.


(T2)rev. < (T2) irrev
as the internal energy of the gas decrease to a larger extent in the case of reversible expansion there
by temperatures

Pirr > Preve at V2

If the same pressure gradient (P1 P2) is creaded in a single step then the piston will come to rest at piont
2 on its our. If piston in stopped at the volume V2 then the single stage expansion will be denoted by the point
2. (As the decrease in tampreatrue will be lesser
Comparision 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 > workdone in one stage
by the gas.
Tf in stage D < Tf in single stage because decrease in internal energy in two stage is > decrease in internal
energy in one stage. Hence two stage expansion will come to rest between the point 2 and 2 but nearly with
point 2.
Adiabatic compression using single-stage & infiete stage compression
(Work done by surrounding)irrerverseble > (Work done by surroundings)reversible
(T2)irrev. > (T1)rev
as internal energy would increase to a greater extent in irreversible path and therefore temp. would also
increase more.

If the same pressure gradiant is created in single stage then the piston would come to rest at point 2 on its
own.
If the piston is taken by single stage. Compression from volume V1 to V2 then the point will be 2

PAGE _ 17
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) , T = T
1 1 1 2

(i) Free expansion Always going to be irrerversible and since Pext = 0

so due = Pext . dV
=0
If no. heat is supplied q = 0

then E = 0 so T = 0.
Ex. A sample of an ideal monoatomic gas initially at (1 L, 10 atm, 300 K) is expanded till its volume becomes 4 L
(a) using reversible isothermal expansion
(b) using by expanding against constant exteranl pressure of 1 atm isothermally.
(c) using reversible adiabatic process
(d) by expanding aganist constant external pressure of 1 atm adiabatically.
(e) by expanding againest constant external pressure of 1 atm under a process in which final pressure of gas
becomes 5 atm.
Calculate work, heat and E in each of the above process.

LECTURE#5
st
Application of Law
U = Q + W W = P V
U = Q PV
(a) Constant volume process
du = dq + dw
du = dq pdv
du = (dq)v
Heat given at constant volume = change in internal energy
du = (dq)
du = (nCdT)v
du = nCvdT
Cv is Specific molar heat capacity at constant volume.
1 du ( dq) 1
CV = = x
n dT dT n
Cv is defined as amount of heat given per degree rise is temperature per mole at constant volume, for an ideal
gas
1 du 1 d ( fnRT ) / 2 f
Cv = . = R
n dT n dT 2
(b) Constant pressure process :
du = dQ + dW
du = dQ . PdV
dQ = du PdV ............... (i)

Defining a new thermodynamic function


H Enthalpy (state function and extensive property)
H = u + Pv
as dH = du + d (Pv)
as P = constant
dH = du + Pdv .............. (ii)

PAGE _ 18
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
Heat capacity at constant pressure

1 dH 1 (dq)p
Cp = =
n dT n dT
* Cp is defined as the amount of heat given to increases the temperature of 1 mole of substance by 1 at
constant pressure.
* This can always be used anywhere.
* Relation between Cp ad 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

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 = 1 nRdT
2

W= Pext. dv
dH = dv + d (Pv)
H = u + nR T
du = dQ + dw

Q.5 Calculate the maximum work done when pressure on 10 g of hydrogen is reduced form 20 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.
Sol. We have,
P1
W = 2.303 nRT log P
2

wt. in grams 10
n = number of moles of hydrogen = mol. wt. = 2 = 5 moles.

20
Thus W = 2.303 5 2 273 log = 8180 calories.
1
further, the change in state of the system is from a gas to a gas and therefore, at constant temperature,
internal energy will not change i.e.,
E = 0.
Again, q = E W = 0 ( 8180 ) = 8180 calories.

PAGE _ 19
Q. Calculate q, w. E & H for processes AB, BC & CD & for whole of the process (for a centain mass of a
monoatomic gas) and also prove that only for isobaric process q = H and only for isochoric precess q =E

P/2

P/4

V 2V 4V
V
Sol.
Ex. A sample of an ideal monoatomic gas initially at (1 L, 10 atm, 300 K) is expanded till its volume becomes 4
L
(a) using reversible isothermal expansion
(b) using by expanding against constant exteranl pressure of 1 atm isothermlly.
(c) using reversible adiabatic process
(d) by expanding aganist constant external pressure of 1 atm adiabatically.
(e) by expanding againest constant external pressure of 1 atm under a process in which final pressure of gas
becomes 5 atm.
In All above processes calculate q us E & H.
Sol.
Ex. Write formula for calulation of q, W E and H. for following process on an ideal gas
(a) Reversible isothermal expansions
(b) Irreversible isothermal expansions (against constant external pressure of Pext )
(c) Reversible adiabatic expanstion
(d) Imerersible adiabatic expansions (against constant external pressure of Pext )
(e) Reversible isocharic process
(f) Reversible isobaric process
(g) Free expansion from Vi Vf
Case - II For solids and liquid system :
f
du = nCvdT nRdT
2

f
dH = nCp dT 1 nRT
2

W= Pext. dv
H = u + (P2V2 P1V1)
du = dq + dw

Ex. A liquid of volume of 100 L and at the external pressure of 10 atm it the is confined inside an adibatic 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
W=1
Sol. work dom = 100 1 = 100 lit atm
q = 0 w = u
100 = u
H = u + (P1V2 P1V1 )
= 100 + (100 99 100 10)
= 100 + 100 89
= 9000 lit atm.
1 lit atm = 101.3 Jule.

PAGE _ 20
Case III: Calculation of q, W, E and H during phase wanstions.
Phase transitions generally take place at constant pressure (unless specified) and at constant temperature.
so T = 0
But stile H and E are non zero (different from process on an ideal gas)
Because during phase transitions thought 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 thermodyanmics

Ex. Calculate q, W, E and H when 90 gm of water at 100C is vapawised into vapour at constant external
pressure of 1 atm. Given that latent heat of vapavisation of water = 540 cal/gm and assume that steam
behaves as are ideal gas. density of water = 1 gm/ml.
Sol.

Ex. Calculate q, W, E and H when 100 gm of calulate form of CaCO3 is comerted into its aragonite form given
density of calculate = 2 gm/CC
density of arangonite = 2.5 gm/CC and
CaCO3 CaCO3
Calcite Arangonite H = 2 kJ/mole
Generally for solid Solid

solid Liquid

a solid Liquid

transitions W << q so. q = H


E ~
while for gaseous conversion for example
Solid gas

Liquid gas
q = H E. as W will be significant

Q.2 Calculate W and E for the conversion of 1 mole of water into 1 mole of steam at a temperature
of 100C and at a pressure of 1 atmosphere. Latent heat of vaporisation of water is
9720 cal/mole.
Sol. P = 1 atm
V1 = volume of 1mole of water at 100C = 18 mL.
V2 = volume of 1 mole of steam at 100C
373
= x 22400 = 30605 mL. (Charless law )
273
Now we have,
30587 101 .3
W = p ( V2 V1 ) = 1 (30605 18) = 30587 atm ml = cal = 741 calories
1000 4.2
Again we have,
E = q + W = 9720 + ( 741) = 8979 calories.

PAGE _ 21
LECTURE # 6
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 direaction on its known by its own system, sorrounding interactions without the
help of any external agency then that direction is known as spontaneous direction and the process is knwon
as a pontaneous 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 0C) although H > 0 , E > 0
* Vaporization of water (above 100C) 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
* It is observed that nature tries to distribute energy and matter uniformaly (randomization)
Second law of thermodynamics :
Entropy of the universe is constanlty 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
ds = or S =
T T
dq is state function only for reversible process
1
dS dqrev , dS
T
At Higher T - entropy is already high. Therefor heat addition will not introduce much change in the entropy.

Entropy calulation :
1. For calculating Ssurrounding : As the surrounding is an infinite heat reservoir hence no. amount of heat
given to the sorrounding can cause turbulance in it, hence all heat exhanges with sorroundings are consid-
ered to be reversible.
dq surroundin g
Ssurrounding = T
For surrounding T is constant
1 q surroundin g
Ssurr = dq surr =

T T
Bu the law of conservation of energy
qsurr = qsystem
q system
Ssurr =
T

PAGE _ 22
(b) For Ssystem

As S is a state function S will not depend on path.


S irrev = S rev
B
dqrev
S = T reversible path .
A

ENTROPY CALCULATION FOR SOLID OR LIQUID SYSTEM.


e.g. Cu block kept in open atmosphera

T2
m.s. dT dq surr
Suniverse = Ssystem + Ssurr =
T T
T1

T2 q surr
Suniverse = m.s. n T + T
1 2

but q surr = qsystem = ms (T2 T1)


= ms (T1 T2)
T2 ms (T1 T2 )
Suniverse = ms n T + T2 >0
1

qA qB
Ssystem = T T
1 2

if qA = q
qB = q
q q
Ssystem = T T 0
1 2

FOR PHASE TRANSFORMATIONS


dq f Q
Sfusion= T
T dq T
Hfus
for constant pressure Sfus. =
T

Ufusion
for constant volume Sfus. =
T

dQ 1 Q
Svap = T dQ

T T

H vap
for constant Pressure, Svap =
T

H vap
for constant Volume, Svap =
T

PAGE _ 23
LECTURE # 7
ENTROPY CALCULATION FOR AN IDEAL GAS UNDERGOING A PROCESS.
irr
State A State B
Sirr

P1, V1, T1 P2, V2, T2


As s is a state function S will not depend upon path
B
dq rev
Sirrev = Srev, system = T rev path.
A

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 = T
A

for an ideal gas


Pgas nR
& du = ncV dT
T V

T2 2 V
nc v dT nRdv
S =
sys
T1
T V
V
1

T2 V2
Ssystem = ncv ln T + nR ln V
1 1

ISOTHERMAL PROCESS :
(a) Reversible
Re v
State A State B
P1,V1,T P2,V2,T
T2 V
S system = nCVln + nRln 2
T1 V1

0
dq system
Ssorrounding =
T
FLOT du = dq + dw
dq = dw
V2
q = w as w = nRTn V
1
V2
q = nRTn V
1

V2
nRTn V2
Ssys. = V1 nRn
T V1

PAGE _ 24
Suniverse= Ssystem + Ssurr

V2 V2
= nRn nRn =0
V1 V1
(b) rreversible
irrev
State A State B
P1,V1,T P2,V2,T
V2
Ssystem = nRn
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 = nRn >0
V1 T

1 V2
= (nRT n ) Pext ( V2 V1 )
T V 1
( wgas )rev ( wgas )irrev

As irrevensible work of gas is less then reversible work.

ADIABATIC PROCESS
(a) Reversible Adiabatic
State A rev
State B
P1,V1, T1 P2,V2, T2
T2 V2
Ssystem = nCV n T + nR n V
1 1

TV1 = constant
1
T2 V1

T1 = V2

1
V1 V2
(S)system = nCVn + nRn V = 0
V2 1

q
S surr = =0; S universe = 0 + 0 = 0
T
(b) Irreversible Adiabatic
State A irre
State B
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

PAGE _ 25
q sys
S surr
= =0 as q = 0
T
For irreversible exparsion 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.

Q. For an ideal gas Cp = 2.5 R, calculate the change in entropy suffered by 3 moles of gas on being heated from
300 K to 600 K at (a) constant pressure (b) constant volume.
T2 P1
Sol. (a) S = nCpn T1 + Rn P2

At constant pressure :
T2
S = n Cpn T1 = 3 2.5 Rn2

= 43.22 JK1 mol1.


(b) At constant volume :
T2
S = nCVn T1 = 3 1.5 Rn2

= 25.93 JK1 mol1.

Q. (a) One mole of an idal gas expands isothermally and reversibly at 25C from a volume of 10 litres
to a volume of 20 litres.
(i) What is the change in entrogy 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 10L volume.

V2 20
Sol. (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, E = 0 and heat is absorbed by the gas,
qrev = E W = 0 (1718) = 1718 J.
qrev = 1718 J. ( process is reversible)
1718
(iv) DSsurr= = 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 entrogy of the system plus surroundings increases by 5.76 J/K, as we expect entropy to increase in
an irreversible process.

PAGE _ 26
LECTURE # 8

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 S .
These values are tabulated : S = Sproducts Sreactants.

Entropy calculation For chemical reaction

aA + bB cC + dH

0 0
S0system = ( ni Sm )product ( ni Sm )reactant
0
where Sm = 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

Gibbs free energy G) :


A system parameter to prodict the spontitancity of chemical reaction was introduced by Gibbs so that
entropy calculation for the surrounding need not be carried out.
for a spontaneous change

Sunivense = Ssystem + Ssurrounding


Q system Hsystem
Ssurr = =
T T
TS univ = TS system Hsystem

Introducing a new thermodyamic function G = Gibbs free energy (State function and an extensive property)
Gsystem = H system TS system
G = H TS
Gsystem = H system TS system .................. (ii)

Comparing equation (i) and (ii)


Gsystem = TS universe
New critatria of spontancity :
(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
G system S system G system = H system TS system
+ Ve Ve +
Ve + Ve
+ Ve + Ve Ve at high temprature
Ve Ve + Ve at high temprature

PAGE _ 27
G = standrad free energy change :
When the reactants under standrad conditions gets converted into products which is also under standered
condition, then the free energy change is known as G (it is a contant) for 1 mole at 1 bar.

At standered conditions :
G = H TS
= constant for a GIVEN REACTION
AB C + D
G = (Gbbs energy of product) (Gibbs energy of reactant)
0 0 0 0 0 0
G = Gm ,C + Gm,D Gm,A G m,B , where Gm can not be calculated as Hm cannot be calculated.

hence, we can convert this relation in to Gibbs energy of formation of substance.


G = G0f ,C + G0f ,D G0f ,A G 0f ,B

G0f : standered Gibbs energy of formation.

G0f (elements in their standard states) = 0

G = G0f ,product G0f ,reac tan ts


For a reaction in progress
G = G + RT n Q
Q is reaction quotient , G > 0 backward is feasible , G < 0 forward is feasible
At equilibrium G = 0 Q = K G = RT n K at equilibrium

Physical interpretation of G.
The free energy change of a process symbolises the maximum amount of non-expansional (compression)
work which can be performed.
du = dq + dw
du = dq + dwexpon + dwexp
dwnon-exp = du dq dwexp

dwnon-exp = du dq + PdV dwnon-exp = dH dq

For maximum work of non expansion the process should be reversible isobaric.

dq = dqrev = T.dS
dwnon-exp = dH TdS = G

Gibbs -Helmholtz equations :


It interrelates G snd H at constant pressure :

( G) G H ( G ( G)
G = H + T T or = T or S = dT
p T p p

E cell
S = nF T (G = nEF)
p

E cell S
Thus temperature coefficient of the emf of a cell is T =
p nF

Q. At what temperature, will the following process would not be spontaneous ?


A(g) A ()
H = 20 kJ S = 50 J/K
(A) > 200 K (B) > 300 K (C) 350 K (D*) > 400 K

PAGE _ 28
Sol. G > 0
H > TS
H
T < S [Since H & S both are negative]

H
or T > or T > 400 K
S

Q. Find whether the given reaction is spontaneous at 1 atm & 298 K.


1
Ag(s) + Cl (g) AgCl(s)
2 2
Given Hf (AgCl) = 127 KJ and S of AgCl(s), Ag(s) and Cl2(g) are 96, 42.7 & 223 JK1mol1 respectively.
223
Sol. S = 96 42.7 = 58.2 JK1
2
G = H TS
= 127 103 + 298 58.2
= 109.65 103
So spontaneous.

Q. Ka for CH3COOH at 25C is 1.754 10-5 . At 50C, Ka is 1.633 10-5 What are H and S for the
ionisation of CH3COOH?
Sol. (G)298 = 2.303RT log K = 2.303 8.314 298 log (1.754 10-5)
= 27194 J.
(G)323 = 2.303 8.314 323 log ( 1.633 10-5)
= 29605 J.
G = H TS
27194 = H 298 S
29605 = H 323 S
H = 1.55 kJ/mol
S = 96.44J/mol.K

LECTURE#9
THERMOCHEMISTRY :
Deals primarily with the transfer of heat between a chemical system and its surroundings when a charge of
phase or a chemical reaction takes place with the system.
In laboratory, the majority of chemical reactions takes place under the constant atmospheric pressure so
heat transfer is equal to the change in the enthalpy of the system. However if any reaction is carried out at
constant volume, then heat transfer will be equal to charge in internal energy of the system.
Enthalpy of a substance :
Every substance has a fixed value of enthalpy under any particular state. Through 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 works enthalpy can be considered as heat constant (amoiunt)
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.

PAGE _ 29
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 contant initially be Hm ,1 & finally entalpy contant be Hm , 2

0 0
Then H = Hm , 2 Hm ,1
= heat added at constant pressure to change temperature from 25C to 50C.
= CPT = (18 cal/mole C) (25C) = 450 cal
Q.7 Why does heat get released/absorbed during chemical reactions?
Ans. 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 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 :
Hreaction = Hproducts Hreactants
Hreactions = Hproducts Hreactants
= positive endothermic
= negative exothermic
Ex. Calculate H of the reaction
2NH3 (g) N2 (g) + 3H2 (g)
Given that the molar entalpy contents (hypothetical) are
Hm (NH3,g) = 200 cal/mole
Hm (H2,g) = 100 cal/mole
Hm (N2,g) = 120 cal/mole

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 , ) = 0
Hf (S, rhombic) = 0 Hf (S, monoclinic) 0
Hf (P, white) = 0 Hf (P, black) 0

PAGE _ 30
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) + Br (l) HBr(g)
2 2 2

0 0 1 0 1 0
Hf(HBr, g) = B Hm (B) = Hm (HBr, g) H (H , g) Hm (Br2, 1) ...(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).

Ex. Calculate the standard enthalpy of reaction ZnO(s) + CO(g) Zn(s) + CO2 (g).
Given, Hf (ZnO, s) = 350 KJ / mole1
Hf (CO2, g) = 390 KJ / mole
Hf (CO, g) = 110 KJ / mole

HESSS 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 algbraic 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, it follows that 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 Hesss law is considerable. In almost all the thermichemical numericals, some way or the other,
Hesss law is used. One of the important applications of Hesss 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

PAGE _ 31
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) r H 1

1
CO(g) + O (g) CO2(g) r H 2
2 2
Substracting the latter from the former, we get

1
C(graphite) + O (g) CO(g)
2 2
Consequently, rH = rH 1 rH 2

LECTURE#10
LATTICE ENERGY OF A CRYSTAL (BORN-HABER CYCLE) :
The lattice energy is defined as the energy required to completely separate one mole of a solid ionic compound
into gaseous ions.The larger the lattice energy, the more stable the ionic compound and the more tightly the
ions held.Consider the following sequence of steps for the formation of NaCl crystals from Na(s) and Cl2(g)
(i) Vaporization of Na(s) Na(s) Na (g) Hsub
(ii) Ionization of Na(g) Na(g) Na (g) + e
+
Hion
1
(iii) Dissociation of chlorine Cl (g) Cl (g) Hdiss
2 2
(iv) Formation of Cl (g) Cl(g) + e Cl (g) Helectron gain
(v) Condensation of Na+(g)
and Cl (g) Na+(g) + Cl(g) NaCl(s) Hlattice

1
Net change : Na(s) + Cl (g) NaCl(s) Hf
2 2
Hesss law, we can write Hf = Hsub + Hion + Hdiss + Helectron gain + Hlattice
All other enthalpies can be determined experimentally.Hence, Hlattice can be determined from the above
relation. The lattice energy is the negative of Hlattice value.

Q. Set up a Born-Haber cycle to find the lattice energy of NaCl crystal. Given Hf (NaCl) = 410 kJ mol1 .
Ionization enthalpy of Na = 495 kJ mol1 , electron affinity of chlorine = 365 kJ mol1 , sublimation enthalpy of
Na = 315 kJ mol1 and dissociation enthalpy of Cl2(g) = 240 kJ mol1 .

Q. from the following thermochemical equation, calculte the enthalpy of formation of cane sugar (C12H22O11) :
(i) C12 H22 O11 (s) + 12 O2(g) 12 CO2(g) + 11H2O() H = 5650 kJ mol1

(ii) C(s) + O2 (g) CO2(g) H = 390 kJ mol1

1
(iii) H2 (g) + O (g) H2O() H = 285 kJ mol1
2 2

Q. From the datat at 25C


(i) Fe2O3(s) + 3C(graphite) 2Fe(s) + 3CO(g) H = 490 kJ mol1

(ii) FeO(s) + C(graphite) Fe(s) + CO(g) H = 155 kJ mol1

(iii) C(graphite) + O2 (g) CO2(g) H = 390 kJ mol1

1
(iv) CO(g) + O (g) CO2(g) H = 280 kJ mol1
2 2

PAGE _ 32
Q.8 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.
Sol. Given that

1
(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.

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 298.15 K is 890.36 kJ mol1. This implies
the following reaction :
CH4 (g) + 2O2(g) CO2(g) + 2H2O () H = 890.36 kJ mol1
The standard enthalpy of combustion of methane at 298.15 K may be written as
Hc (CH4, g, 29815 K) = 890.36 kJ mol1
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) + 2Hf(H2O , ) Hf (CH4, g)
therefore
Hf(CH4, g) = Hf(CO2, g) + 2Hf(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)
= [ 393.51 + 2 (285.83) (890.36)] kJ mol1
= 74.81 kJ mol1
or, equivalently, we may add the following three chemical equations.
C(graphite) + O2 (g) CO2 (g) CH = 393.51 kJ mol1
1
2 [H2(g) + O (g) H2O()] rH = 2( 285.83) kJ mol1
2 2
[CH4(g) + 2O2 (g) CO2 (g) + 2H2O()] rH = ( 890.36) kJ mol1

C(graphite) + 2H2(g) CH4 (g) fH = 74.81 kJ mol1

PAGE _ 33
Ex. Calculate the entalpy change of the following reaction
2C2H2(g) C6H6(g)
Given Enthalpy of combustion of C2H2(g) = 1.30 MJ mol1 and that of C6H6(g) = 3.30 MJ mol1

Ex. Using the combustion data given below, compute the enthalpy of formation of isoprene (g) and its resonance
energy. Given Hf (from bond enthalpies) = 103 kJ mol1
Data : Enthalpy of combustion of isoprene (g) HC = 3120 kJ mol1
Enthalpy of formation of CO2 (g) Hf = 393 kJ mol1
Enthalpy of formation of H2O() Hf = 285 kJ mol1

MEASUREMENT OF ENTHALPY OF COMBUSTION :


Enthalpies 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 calorimetre
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 calorimetre.

If total heat capacity of calorimeter and all of its contents = C, rise in temperature = T then heat released =

M
q = CT of this heat is because of mass m if substance then due to 1 mole heat released = q
m
= EC (constant volume reactions) 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.

Q. A 0.12 g sample of solid magnesium( molar mass = 24 gmole1) is burned in a constant volume bomb
calorimeter that has a heat capacity of 1.5 kJ 0C1.The calorimeter contains 300 mL of water ( density 1g mL
1
) and its temperature is raised by 1 0C. Calculate the enthalpy of combustion of magnesium at 300K.

Q.9 A gas mixture of 3.67 litres of ethylene and methane on complete combustion at 25C produces
6.11 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 1423 and 891 kJ mol-1 at 25C. [ IIT 1991 ]
3.67 lit.
Sol. + O2 CO2 + H2O
C2H4 + CH4

x lit. (3.67 x)lit. 6.11 lit.


(say)
or x moles (3.67 x) moles 6.11 moles

PAGE _ 34
Applying POAC for C atoms,
2 x + 1 ( 3.67 x ) = 1 6.11; x = 244 lit.
Thus, the volume of C2H4 = 2.44 lit., and volume of CH2 = 1.23 lit.

2.44
volume of C2H4 in a 1litre mixture = = 0.665 lit.
3.67
and volume of CH4 in a 1 litre mixture = 1 0.665 = 0.335 lit.
Now, thermochemical reactions for C2H4 and CH4 are
C2H4 + 3O2 2CO2 + 2H2O; H = 1423 kJ
CH4 + 2O2 CO2 + 2H2O; H = 891 kJ
As H values given are at 25C, let us first calculate the volume occupied by one mole of any gas at 25C
(supposing pressure as 1atm)
298
Volume per mole at 25C = 22.4 = 24.45 lit.
273

1423
Thus, heat evolved in the combustion of 0.665 lit. of C2H4 = 0.665 = 38.70 kJ
24.45

891
and heat evolved in the combustion of 0.335 lit.of CH4 = 0.335 = 12.20kJ.
24.45
total heat evolved in the combustion of 1 litre of the mixture = 38.70 + (12.20) = 50.90kJ.

LECTURE#11
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 mol1

indicates that when 1 mol 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 mol1

(ii) HCl(g) + 40 H2O() HCl (40H2O) H3 = 73.0 kJ mol1

(iii) HCl(g) + 200 H2O() HCl (200H2O) H4 = 74.2 kJ mol1

(iv) HCl(g) + aq HCl (aq) H5 = 75.0 kJ mol1


Whenever amount of solvent is not specified then take its amount to be very large just like in
equation no. (iv).

ENTHALPY OF DILUTION :
The enthalpy of dilution is the change in enthalpy when a solution containing 1 mole of solute is diluted from
one concentration to another for example for the reaction
HCl . 40 H2O + aq HCl (aq), the enthalpy change can be calculated as follows
HCl (g) + aq HCl (aq) H 1 = 75 kJ mol1
HCl(g) + 40 H2O HCl . 40H2O H 2 = 73 kJ mol1
Subtracting, we have HCl . 40 HCl + aq HCl (aq) H = 2 kJ mol1

PAGE _ 35
ENTHALPY OF HYDRATION :
Enthalpy of hydration is used in following to ways.
(i) Enthalpy of hydration of anhydrous or partially hydrated salts.
(ii) Enthalpy of hydration of gaseous ions.

(i) 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 mol1
CuSO4 . 5H2O (s) + 795 H2O () CuSO4 (800 H2O) Hr = + 10 kJ mol1
by subtraction, we get CuSO4(s) + 5H2O () CuSO4 . 5 H2O(s)Hr = 78 kJ mol1

(ii) 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) H =

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

for SA + SB this 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
mol1. 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 mol1
CH3COOH + Na OH Na + CH3COO + H2O rH = 49 kJ mol1
+ +

The enthalpy of ionization can be calculated as follows. The neutralization of a weak acid, say HCN, may be
represented in two steps, namely,

(i) Ionization HCN H+ + CN H1 = x

(ii) Neutralization H+ + OH H2O H2 = 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 = H1 + H2
H1 = HH2 = [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.

PAGE _ 36
Ex. 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.
Sol. 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 mol1 = 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 mol1
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 mol1
Subtracting, we have, C(graphite) C(diamond) Htrs0 = 1.90 kJ mol1

ENTHALPY OF PRECIPTION :
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 mol1

ENTHALPY OF FORMATION OF IONS :


The enthalpy change when one mole of hydrated ions is obtained from element in its standard state as.
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 mol1
For this reaction, Hr = Hf (H2O,l ) {Hf (H ,aq) + Hf (OH,aq)}
0 0 0 + 0

Hence at 25 C, we get Hf0 (H+, aq) + Hf0 (OH ,aq) = Hf0 (H2O, l ) Hr0
0

so Hf0 (OH ,aq) = { 286.1 ( 57.1)} kJ mol1 = 229.00 kJ mol1


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 mol1
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 mol1
= 240.12 kJ mol1
Similarly, from NaCl(aq) or HCl(aq), the enthalpy of formation of Cl(aq) can be determined, and so on. These
are recorded in Appendix-II. 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.

Ex.1 The enthalpy of formation of H2O(l) is 285.83 kJ mol1 and enthalpy of neutralization of a strong acid and a
strong base is 55.84 kJ mol1. What is the enthalpy of formation of OH ions ?
Sol. Given that
H+(aq) + OH(aq) H2O()
f H 0 285.83 kJ mol1
neutH = fH(H2O, ) fH(OH, aq)
Hence fH (OH, aq) = fH(H2O, ) neutH
= [285.83 (55.84)] kJ mol1
= 229.99 kJ mol1

PAGE _ 37
Ex.2 Calculate H for the reaction
Ag+(aq) + Cl(aq) AgCl(s)
at 25C. Given fH (Ag+, aq) = 105.58 kJ mol1, fH (Cl, aq) = 167.16 kJ mol1
and fH(AgCl, s) = 127.07 kJ mol1
Sol. For the reaction
Ag+(aq) + Cl(aq) AgCl(s)
we have
H = fH (AgCl, s) fH(Ag+, aq) fH(Cl, aq)
= [127.07 105.58 (167.16)] kJ mol1
= 65.49 kJ mol1
Ex.3 Calculate the enthalpy change when one mole of HCl(g) is dissolved in a very large amount of water at 25C.
The change in state is HCl(g) + aq H+(aq) + Cl(aq)
Given : fH(HCl, g) = 92.31 kJ mol1 and fH (Cl, aq) = 167.16 kJ mol1
Sol. For the reaction
HCl(g) + aq H+(aq) + Cl(aq)
we have
H = H(Cl,aq) fH(HCl, g)
H = [167.16 (92.31)] kJ mol1
= 74.85 kJ mol1

LECTURE#12
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 OH 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 mol1
However, to break the OH bond in the hydroxyl radical required a different quantity of heat :
OH(g) O(g) + H(g) Hr0 = 423.38 kJ mol1
The bond enthalpy, OH, is defined as the average of these two values, that is :

501.87mol 1 423.38kJmol 1
OH = = 462.625 kJ mol1
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) H H = Hr0 = 435.93 kJ mol1
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
C2H4(g) + HCl(g) C2H5Cl(g) (g)
be required from the bond enthalpy data. This may be calculated as follows :

Enthalpy required to Enthalpy released to



H = break reactants into form products from the
gasesous atoms gasesous atoms
= [4CH + C=C + HCl] + [5CH CC CCl]
= (C=C + HCl) (CH + CC + CCl)

RESONANCE ENERGY :
Hresonance = Hf, experimental Hf, calclulated
= Hc, calclulated Hc, experimental

PAGE _ 38
Q.10 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 C
Sol. We have to calculate H for the reaction C C
H = ?
6C (s) + 3H2(g) C6 H6 (g) C C
For reactants : C
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 CC = 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.,
H = 6 170.9 + 6 52.1 6 99 3 83 140 = 75.0 kcal

Ex.4 Find the bond enthalpy of S S bond from the following data :
C2H5 S C2H5(g) fH = 147.23 kJ mol1
C2H5 S S C2H5(g) fH = 201.92 kJ mol1
S(g) fH = 222.80 kJ mol1
Sol. Given that

(i) 4C(s) + 5H2(g) + S(s) C2H5 S C2H5(g) fH = 147.23 kJ mol1

(ii) 4C(s) + 5H2(g) + 2(s) C2H5 S S C2H5(g) fH = 201.92 kJ mol1


Subtracting Eq. (i) from Eq. (ii), we get

C2H5 S C2H5(g) + S(s) C2H5 S S C2H5(g) fH = 54.69 kJ mol1


Adding to this, the following equation

S(g) S(s) fH = 222.80 kJ mol1


We get

C2H5 S C2H5(g) + S(g) C2H5 S S C2H5(g) fH = 277.49 kJ mol1


In the last equation 277.49 kJ of heat id evolved because of the SS bond formation.
Hence, the bond enthalpy of S S is 277.49 kJ mol1.

Diagrammatically, we may represent the above calculation as follows :

H H H H H H H H
| | | | | | | |
H
H C C S C C H(g) + S(s) H C C S S C C H(g)
| | | | | | | |
H H H H H H H H
2C C + 10C H vapH(S) -2C C - 10C H
+ 2C S -2C S - S S

H H H H

4C(g) + 10H(g) + S(g) + S(g) H C C S S C C H

H H H H

PAGE _ 39
According to Hesss law
H = Enthalpy involved in bond breaking Enthalpy involved in bond making
= [2C C + 10CH + 2CS + Dvap H(S)] + [2CC 10CH 2CS SS]
= vapH(S) SS
or SS = vapH(S) H
= vapH(S) [fH(C2H5 S S C2H5] fH(C2H5 S C2H5)]
= [222.80 {201.92 (174.23)}] kJ mol1
= 277.49 kJ mol1

Ex.5 Using the bond enthalpy data given below, calculate the enthalpy change for the reaction

C2H4(g) + H2(g) C2H6(g)


Data :
Bond Bond enthalpy
CC 336.81 kJ mol1
C=C 606.68 kJ mol1
CH 410.87 kJ mol1
HH 431.79 kJ mol1
Sol. Diagrammatically, we any 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

The heat required to dissociate C2H4(g) and H2(g) into the gaseous atoms is
For breaking 1C=C 606.68 kJ mol1
For breaking 4CH 4 x 410.87 kJ mol1
For breaking 1HH 431.79 kJ mol1

Total 2681.95 kJ mol1

Thus H = 2802.03 kJ mol1 + 2681.95 kJ mol1 = 120.08 kJ mol1


Ex.6 From the following data :
Enthalpy of formation of CH3CN = 87.86 kJ mol1
Enthalpy of formation of C2H6 = 83.68 kJ mol1
Enthalpy of sublimation of graphite = 719.65 kJ mol1
Enthalpy of dissociation of nitrogen = 945.58 kJ mol1
Enthalpy of dissociation of H2 = 435.14 kJ mol1
C H bond enthalpy = 414.22 kJ mol1
Calculate (i) C C and (ii) C N
Sol. (i) C C : We have
C2H6(g) 2C(graphite) + 3H2(g) H1 = 83.68 kJ mol1
2C(graphite) 2C(g) H2 = 2 x 719.65 kJ mol1
3H2(g) 6H(g) H3 = 3 x 435.14 kJ mol1
Adding, we get
C2H6(g) 2C(g) + 6H(g) H4 = 2828.4 kJ mol1

PAGE _ 40
Now H4 = CC + 6CH
Therefore
CC = [2828.4 6 x 414.22] kJ mol1 = 343.08 kJ mol1
Diagrammatically, the above calculations may be represented as follows :
H H
| |
fH C C
2C(graphite) + 2H2(g) H H
| |
H H
H2 H3 -6C H - C C

H H

2C(g) + 6H(g) H C C H

H H
Applying Hesss law, we get
fH = H2 + H3 6CH CC
83.68 kJ mol1 = (2 x 719.65 + 3 x 435.14 6 x 414.22) kJ mol1 CC
CC = (1439.3 + 1305.42 2485.32 + 83.68) kJ mol1
= 343.08 kJ mol1
(ii) C N : We have
3 1
CH3CN(g) 2C(graphite) + H (g) + N2(g) H1 = 87.86 kJ mol1
2 2 2

2C(graphite) 2C(g) H2 = 2 x 719.65 kJ mol1


3 3
H (g) 3H(g) H3 = x 435.14 kJ mol1
2 2 2
1 1
N (g) N(g) H4 = x 945.58 kJ mol1
2 2 2
Adding, we get
CH3CN(g) 2C(g) + 3H(g) + N(g) H5 = 2476.94 kJ mol1
Now H5 = CC + 3CH + C N
Therefore
C N = [2 476.94 3 x 414.22 343.08] kJ mol1 = 891.2 kJ mol1

Diagrammatically, the above calculations may be represented as follows :


H
fH |
2C(graphite) + 3/2H2(g) + 1/2 N2(g) H C C N(g)
|
H
H2 H3 H4 3CH CC
C C
H

2C(g) + 3H(g) + N(g) H C C H

H
Applying Hesss law, we get
fH = H2 + H3 + H4 (3CH + CC + CN)
3 1
87.86 kJ mol1 = 2 x 719.65 + x 435.14 + x 945.58 3 x 414.22 343.08 C N
2 2
C N = (1439.30 + 652.71 + 472.79 1242.66 343.08 87.86) kJ mol1
= 891.2 kJ mol1

PAGE _ 41
Ex.7 Calculate the bond enthalpy C H from the following data at 298 K :
Enthalpy of combustion of methane H = 890.36 kJ mol1
Enthalpy of combusion of C(graphite) H = 393.51 kJ mol1

1
H2(g) + O (g) H2O() H = 285.85 kJ mol1
2 2
Enthalpy of dissociation of H2(g) H = 435.93 kJ mol1
Enthalpy of sublimation of C(graphite) H = 716.68 kJ mol1
Sol. We have

(i) CH4(g) + 2O2(g) CO2(g) + 2H2O() H298K = 890.36 kJ mol1

(ii) C(graphite) + O2(g) CO2(g) H298K = 393.51 kJ mol1

1
(iii) H2(g) + O (g) H2O() H298K = 285.85 kJ mol1
2 2

(iv) H2(g) 2H(g) H298K = 435.93 kJ mol1

(v) C(graphite) C(g) H298K = 716.68 kJ mol1


If we do the following manipulations
Eq. (i) Eq. (ii) 2Eq. (iii) + 2Eq. (iv) + Eq. (v)

We get CH4(g) C(g) + 4H(g)


The corresponding H298K is given is given by
H298K = [890.36 + 393.51 + 2 x 285.85 + 2 x 435.93 + 716.68] kJ mol1
= 1 663.39 kJ mol1
that is, 1 663.39 kJ is required to dissociate one mole of CH4(g) into gaseous atoms in which 4 mol of C H
bonds are broken. Therefore

1663.39 kJ mol 1
CH = = 415.85 kJ mol1
4
Ex.8 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 mol1


Bond enthalpy of C C bond = 347.69 kJ mol1
Bond enthalpy of C = C bond = 615.05 kJ mol1
Enthalpy of sublimation of carbon (graphite) = 718.39 kJ mol1
Enthalpy of dissociation of H2(g) = 435.97 kJ mol1
Sol. For isoprene, we have to form
2C C bonds ; 2C = C bonds and 8C H bonds
For which energy released is
[2(347.69) + (615.05) + 8(413.38)] kJ mol1 = 5 232.52 kJ mol1
that is, H (from gaseous atoms) = 5 232.52 kJ mol1
The reaction corresponding to this is
5C(g) + 8H(g) C5H8(g) fH1 = 5232.52 kJ mol1
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 mol1
5C(graphite) 5C(g) rH3 = 5 718.39 kJ mol1
4H2(g) 8H(g) rH4 = 4 435.97 kJ mol1
Adding, we get
5C(graphite) + 4H2(g) C5H8(g) fH = 103.31 kJ mol1

PAGE _ 42
Diagrammatically, the above calculations may be represented as follows.
fH
5C(graphite) + 4 H2(g) CH2 = C CH2(g)

5fH3 4fH4 CH3


2C=C 2CC 8C
5C(g) + 8H(g)
Applying Hesss law, we get
f H = 5H3 + 4H4 2C = C 8C H
= (5 x 718.39 + 4 x 435.97 2 x 615.05 2 x 347.69 8 x 413.38) kJ mol1
= 103.31 kJ mol1

LECTURE#13
Ex.9 Calculate the resonance energy of benzene compared with one Kekule structure. Given the following data
fH(methane, g) = 74.85 kJ mol1
fH(ethane, g) = 84.68 kJ mol1
fH(ethylene, g) = 52.3 kJ mol1
fH(benzene, g) = 82.93 kJ mol1
Enthalpy of sublimation of carbon (graphite) = 718.39 kJ mol1
Dissociation enthalpy of H2 = 435.89 kJ mol1
Sol. In order to calculate the resonance energy of benzene, we need to compute fH from the bond enthalpy
data. For this, we need C C, C = C and C H bond enthalpies. These can be calculated as follows :
(i) Bond enthalpy of C H from fH (methane) : We have
CH4(g) C(graphite) + 2H2(g) H = +74.85 kJ mol1
C(graphite) C(g) H = +718.39 kJ mol1
2H2(g) 4H(g) ; H = 2 x 435.89 kJ mol1
Adding, we get,
CH4(g) C(g) + 4H(g) H1 = 1 665.02 kJ mol1
Now H1 = 4CH, therefore

1665.02 kJ mol 1
CH = = 416.255 kJ mol1
4

(ii) Bond enthalpy of C C from fH(ethane) : We have


C2H6(g) 2C(graphite) + 3H2(g) H = 84.68 kJ mol1
2C(graphite) 2C(g) H = 2 x 718.39 kJ mol1
3H2(g) 6H(g) H = 3 x 435.89 kJ mol1
Adding, we get
C2H6(g) 2C(g) 6H(g) H2 = 2 829.13 kJ mol1
Now H2 = CC + 6CH
Thus CC = [2 829.13 6 x 416.255] kJ mol1 = 331.60 kJ mol1

(iii) Bond enthalpy of C = C from fH (ethylene) : we have


C2H4(g) 2C(graphite) + 2H2(g) H = 52.3 kJ mol1
2C(graphite) 2C(g) H = 2 x 718.39 kJ mol1
2H2(g) 4H(g) H = 2 x 435.89 kJ mol1
Adding, we get
C2H4(g) 2C(g) + 4H(g) H2 = 2 256.26 kJ mol1
Now H3 = C=C + 4CH

PAGE _ 43
Therefore
CC = [2 256.26 4 x 416.255] kJ mol1 = 591.24 kJ mol1

(iv) fH (benzene) from the bond enthalpy data : We have


6C(g) + 6H(g) C6H6(g) H = (3CC + 3C=C + 6CH)
= 5 266.05 kJ mol1
6C(graphite) 6C(g) H = 6 x 718.39 kJ mol1
3H2(g) 6H(g) H = 3 x 435.89 kJ mol1
Adding, we get
6C(graphite) + 3H2(g) C6H6(g) H2 = +315.96 kJ mol1

(v) Resonance energy of benzen(g) :


Actual value of fH = 82.93 kJ mol1
Calculated value of fH = 351.96 kJ mol1
Thus, benzene becomes more stable by +269.03 kJ mol1. Therefore, its resonance energy is 269.03 kJ mol1.

Ex.10 The enthalpy of formation of ethane, ethylene and benzene from the gaseous atoms are 2 839.2, 2 275.2
and 5 536 kJ mol1, respectively. Calculate the resonance energy of benzene, compared with one Kekule
structure. The bond enthalpy of CH bond is given as equal to 410.87 kJ mol1.
Sol. Bond enthalpy of C C bond = Enthalpy required to break C2H6 into gaseous
atoms 6 x Bond enthalpy of C H bond
= 2 839.2 kJ mol1 6 x 410.87 kJ mol1
= 373.98 kJ mol1
Bond enthalpy of C = C bond = Enthalpy required to break C2H4 into gaseous
atoms 4 x Bond enthalpy of C H bond
= 2 275.2 kJ mol1 4 x 410.87 kJ mol1
= 631.72 kJ mol1
For the formation of benzene having Kekule structure, we have to form 3C C bonds,
3C = C bonds and 6 C H bonds for which enthalpy released is
[3(373.98 + 3 (631.72) + 6 (410.87) kJ mol1 = 5 482.32 kJ mol1
But the given value of fH is
fH(actual) = 5 536 kJ mol1
Hence the resonance energy of benzene compared with one Kekule structure
= fH (actual) fH (Kekule structure)
= (5 536 + 5 482.32) kJ mol1
= 53.68 kJ mol1

RELATION BETWEEN ENERGY AND ENTHALPY OF A REACTION :


rH = rU + (vg)RT
where vg is the change in the stoichiocmetric number of gaseous species in going from reactants to
products.
It should be noted that while computing vg of a reaction, only the stoichiometric numbers of gaseous is
counted and those of liquids and solids are completely ignored.
Case - III For chemical reactions :
aA (s) + bB() + cC(g) aA(s) + bB () + c C (g)

W = Pext. dv
= P ext. v f v i
= Pext. [(VA(s) + (VB() + (VC(g)
(VA(s) + (VB() + (VC(g)]
= W = Pext. [VC(g) VC(g)]

n c 'RT n c RT Pext. (nc ' nc )RT


= Pext. P =
ext P ext Pext.
W = (nc nc)RT

PAGE _ 44
W = ng RT
du = dq + dw
if at constant pressure
dq = dH
du = dH pdv
du = dH ng RT
dH = du + ng RT

KIRCHOFFS EQUATION
(Variation of H 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 Kirchoffs Equations.
P + Q R + S
at temperature T1 let the standard enthalpy of reaction be H1 , then
H1 = Hm (R,T1) + Hm (S, T1) Hm (P, T1) Hm (Q, T1)
If the same reaction is carried out at temperature T2, then
H2 = Hm (R,T2) + Hm (S, T2) Hm (P, T2) Hm (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 requirfed 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 P .dT

for example for the reaction


N2 (g) + 3H2 (g) 2NH3 (g)
H2 = H1 + CP (T2 T1)
where CP = 2CP, N3 CP, N2 3CP, H2
* for a constant volume reaction

E 02 E10 C V .dT

0
Ex. Calculate H 400 K for the reaction

1
N (g) + O2 (g) NO2 (g) H0300 K = 35 KJ mole1
2 2
Given , CP (NO2, g) = 35 JK1 mole1
CP (O2, g) = 30 JK1 mole1
CP (N2, g) = 30 JK1 mole1
Ex. If Hm (H2O, , 298 K) = 200 kJ/mole, Hm (H2 ,g,298 K) = 50 kJ/mole, Hm (O2, gas, 298 K) = 80 kJ/mole
(a) Calculate entalpy change of the reaction
2H2 (g) + O2(g) 2H2O() at 298 K
(b) If CP (H2O, ) = 18 cal/mole K and assuming H2, O2 are behaving as ideal gases then calculate enthalpy
change of above reaction at 348 K.

PAGE _ 45