Unit 7

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7.THERMODYNAMICS
1. State the first law of thermodynamics
"Energy can neither be created nor destroyed, but may be converted from one form to
another".
2. Define Hess's law of constant heat summation.
It states that “the enthalpy change of a reaction either at constant volume or constant pressure is the
same whether it takes place in a single or multiple steps”.
3. Explain intensive properties with two examples
The properties which do not depend upon the quantity of matter present in the system are called
Intensive properties Ex. Boiling point, Melting point
4. Define the following terms:
a. isothermal process b. adiabatic process
c. isobaric process d. isochoric process
a. isothermal process : - The thermodynamic process in which temperature remains constant throughout
are called isothermal process.
b. adiabatic process :- The thermodynamic process in which heat exchange between system and
surrounding is not possible.
c. isobaric process :- The thermodynamic process occurring at constant pressure.
d. isochoric process :- The thermodynamic process occurring at constant volume.
5. What is the usual definition of entropy? What is the unit of entropy?
➢ Entropy is a thermodynamic state quantity which is a measure of randomness or disorder of the
system.
➢ The SI unit of entropy is JK−1
6. Predict the feasibility of a reaction when
i) both ΔH and ΔS positive ii) both ΔH and ΔS negative
iii) ΔH decreases but ΔS increases
ΔH ΔS ΔG= ΔH−TΔS Description Example
+ (at low T) non-spontaneous at low
temperature
i, +ve +ve Melting of a solid
− (at high T) spontaneous at high temperature
− (at low T) spontaneous at low temperature
ii, -ve -ve + (at high T) non-spontaneous at high Adsorption of gases
temperature
iii, -ve +ve − (at all T) Spontaneous at all temperature 2O3 (g) ⎯→3O2 (g)
7. Define is Gibb’s free energy.

G is expressed as G = H - TS,
G → Gibb’s free energy ; H → Enthalpy ; T → Temperature ; S → Entropy
Free energy change of a process is given by the relation ΔG= ΔH - TΔS.
8. Define enthalpy of combustion.
➢ The enthalpy change when one mole of any substance is completely burnt in excess of oxygen.
➢ Ex:- the heat of combustion of methane is – 87.78 kJ mol-1
9. Define molar heat capacity. Give its unit.
➢ “The amount of heat absorbed by one mole of the substance to raise its temperature by 1 kelvin”.
➢ The SI unit of molar heat capacity is JK−1mol-1
10. Define the calorific value of food. What is the unit of calorific value?
➢ The calorific value is defined as the amount of heat produced in calories (or joules) when one gram
of the substance is completely burnt.
➢ The SI unit of calorific value is J kg−1.
➢ It is usually expressed in Cal g-1.
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11. Define Heat of neutralization.

➢ It is the amount of heat liberated when one gm-equivalent of acid completely neutralizes by one gm
equivalent of base.
➢ Enthalpy of neutralization for strong acid and strong base is constant . H = –57.27 kJ/mol.
12. What is lattice energy?
It is defined as the amount of energy required to completely remove the constituent ions from its
crystal lattice to an infinite distance. It is also referred as lattice enthalpy.
13. What are state and path functions? Give two examples.
State Function Path Function
A state function is a thermodynamic property of a A path function is a thermodynamic property of the
system, which has a specific value for a given state system whose value depends on the path by which
and does not depend on the path (or manner) by the system changes from its initial to final states.
which the particular state is reached.
Example : Pressure (P), Volume (V), Example: Work (w), Heat (q).
Temperature(T), Internal energy (U),
Enthalpy (H), free energy (G) etc.
14. Give Kelvin statement of second law of thermodynamics.
“It is impossible to construct an engine which operated in a complete cycle will absorb heat from a
single body and convert it completely to work without leaving some changes in the working system”.
15. The equilibrium constant of a reaction is 10, what will be the sign of ΔG? Will this reaction
be spontaneous?
Van’tHoff equation. G = - 2.303RTlogK
Equilibrium constant K = 10  G = - 2.303RTlog10 = - 2.303RT
G is –ve ; so the reaction is Spontaneous.
16. Enthalpy of neutralization is always a constant when a strong acid is neutralized by a
strong base - account for the statement.
The reason for this can be explained on the basis of Arrhenius theory of acids and bases which states
that strong acids and strong bases completely ionise in aqueous solution to produce H+ and OH−ions
respectively.
17. State the third law of thermodynamics.

The entropy of a perfectly crystalline material at absolute zero ( T = 0 K (or) -2730C) is zero.
18. Write down the Born-Haber cycle for the formation of CaCl2
ΔH1 = heat of sublimation of Ca(S)

ΔH2 = dissociation energy of Cl2(g)
ΔH3 = ionisation energy of Ca(S)
ΔH4 = Electron affinity of Cl (g)
ΔH5 = the lattice enthalpy for the formation of CaCl2(S)
ΔHf = enthalpy change for the formation of CaCl2(S) directly form elements
ΔHf = ΔH1 + ΔH2 + ΔH3 + ΔH4 + ΔH5
19. Identify the state and path functions out of the following: a)Enthalpy b)Entropy c) Heat
d) Temperature e) Work f) Free energy.
a) Enthalpy state function
b) Entropy state function
c) Heat path function
d) Temperature state function
e) Work path function
f) Free energy state function
20. State the various statements of second law of thermodynamics.

Entropy statement:-
➢ Entropy is a measure of the molecular disorder (randomness) of a system.
➢ The entropy of an isolated system increases during a spontaneous process.
➢ Entropy is state function
Kelvin-Planck statement:-
“It is impossible to construct an engine which operated in a complete cycle will absorb heat from a
single body and convert it completely to work without leaving some changes in the working system”.
Clausius statement:-
It is impossible to transfer heat from a cold reservoir to a hot reservoir without doing some
work.
Efficiency :-
work performed
Efficiency =
heat absorbed
21.What are spontaneous reactions? What are the conditions for the spontaneity of a process?
Spontaneous reaction:- A reaction that occurs under the given set of conditions without any external
driving force is called spontaneous reaction.
Conditions for the spontaneity : Δ𝐻 = −𝑣𝑒, Δ𝑆 = + 𝑣𝑒, Δ𝐺 = −𝑣𝑒
22.List the characteristics of internal energy.
The internal energy of a system is an extensive property.
The internal energy of a system is a state function.
The change in internal energy of a system is expressed as
U= Uf – Ui
ΔU = Uf − Ui = −ve (Uf < Ui)
ΔU = Uf − Ui = +ve (Uf >Ui)
23.Explain how heat absorbed at constant volume is
measured using bomb calorimeter with a neat
diagram.
➢ For chemical reactions, heat evolved at constant volume,
is measured in a bomb calorimeter.
➢ The inner vessel (the bomb) and its cover are made of
strong steel.
➢ The cover is fitted tightly to the vessel by means of metal
lid and screws.
➢ A weighed amount of the substance is taken in a
platinum cup and pressurized with excess oxygen.
➢ The bomb is immersed in water, in the inner volume of
the calorimeter.
➢ The reaction is started by striking the substance through
electrical heating.
➢ Heat evolved during the reaction is absorbed by the
calorimeter as well as the water in which the bomb is
mmersed.
➢ The change in temperature is measured using a Beckman thermometer. Since the bomb is sealed its
volume does not change and hence the heat measurements is equal to the heat of combustion at a
constant volume (U0c).
➢ The amount of heat produced in the reaction U0c is equal to the sum of the heat abosrbed by the
calorimeter and water.
Heat absorbed by the calorimeter :-
q1 = k T
k - calorimeter constant
k = mcCc
mc- mass of the calorimeter ; Cc- heat capacity of calorimeter.
Heat absorbed by the water :-
q2 = mwCwT
mw- molar mass of water
Cw- molar heat capacity of water (75.29 JK-1mol-1)
U0c= q1 + q2
U0c= kT + mwCwT
= (k +mwCw)T
➢ Calorimeter constant can be determined by burning a known mass of standard sample (benzoic acid)
for which the heat of combustion is known (-3227 kJmol-1) The enthalpy of combustion at constant
pressure of the substance is calculated from the equation .
𝐇𝟎(Pressure) = 𝐔𝟎(volume) + RTn(g)
𝐜 𝐜
24.Calculate the work involved in expansion and compression process.
Work involved in compression processes :
➢ The essential condition for expansion or compression of a system is that there should be difference
between external pressure (Pext) and internal pressure (Pint).
➢ Let us consider a cylinder which contains 'n' moles of an ideal gas fitted with a frictionless piston of
cross sectional area A.
➢ The total volume of the gas inside is Vi and pressure of the gas inside is (Pint)
➢ If the external pressure (Pext) is greater than (Pint), the piston moves inward till the pressure inside
becomes equal to (Pext).
➢ Let this change be achieved in a single step and the final volume be Vf.
➢ In this case, the work is done on the system (+w). It can be calculated as follows
W = - F.x …..(1)
where x is the distance moved by the piston during the compression and F is the force
acting on the gas.
F = Pext .A ….(2)
Substituting (2) in (1)
W = - Pext .A.x
A.x = change in volume
A.x = (Vf – Vi)
W = - Pext .(Vf – Vi) -V = (Vf – Vi)
W = - Pext .-V
W = Pext .V
Since work is done on the system, it is a positive quantity.
If the pressure is not constant,
At each stage of compression, the volume decreases by an infinitesimal amount, dV.
In such a case we can calculate the work done on the gas by the relation
In a compression process, Pext the external pressure is always greater than the pressure of the
system.
(Pext) = (Pint+ dP)
Work involved in expansion processes:-

➢ In an expansion process, the external pressure is always less
than the pressure of the system
(Pext) = (Pint−dP)
➢ When pressure is not constant and changes in infinitesimally
small steps (reversible conditions) during compression from
Vi to Vf , the P-V plot looks like in the fig
➢ Work done on the gas is represented by the shaded area.
➢ In general case we can write, (Pext) = (Pint + dP). Such processes are called reversible
processes.
➢ For a compression process work can be related to internal pressure of the system under
reversible conditions by writing equation.
➢ For a given system with an ideal gas
➢ If (Vf > Vi) (expansion), the sign of work done by the process is negative.
➢ If (Vf < Vi) (compression) the sign of work done on the process is positive.
25.Derive the relation between ΔH and ΔU for an ideal gas. Explain each term involved in the
equation.
When the system at constant pressure undergoes changes from an initial state with H1, U1 and V1 to a
final state with H2, U2 and V2 the change in enthalpy ΔH, can be calculated as follows:
H = U + PV
In the initial state 
H1 = U1 + PV1 …….(1)
In the final state 
H2 = U2 + PV2 …….(2)
change in enthalpy is (2) - (1) 
(H2 -H1) = (U1 – U2) + P(V2-V1)
H = U + PV …. (3)
Consider a closed system of gases which are chemically reacting to form gaseous products at constant
temperature and pressure with V1 and V2 as the total volumes of the reactant and product gases
respectively, and n1 and n2 as the number of moles of gaseous reactants and products, then,
For reactants (initial state) :

PV1 = n1RT ….. (4)
For products (final state) :
PV2 = n2RT ….. (5)
(5) – (4) 
P(V2-V1) = (n2-n1) RT
PV = n(g)RT ….. (6)
Substituting (6) in (3)
H = U + n(g)RT …. (7)
H- Change in Enthalpy ;U – Change in Internal Energy ;
n(g) – Change in number of Moles ; R- Gas constant ; T- Temperature.
26.Suggest and explain an indirect method to calculate lattice enthalpy of sodium chloride
crystal.
ΔH1 = Heat of sublimation of Na(S)

ΔH2 = Ionisation energy of Na(S)
ΔH3 = Dissociation energy of Cl2(g)
ΔH4 = Electron affinity of Cl (g)
U = The lattice Energy of NaCl(S)
ΔHf = Enthalpy change for the formation of NaCl(S) directly form its elements
ΔHf = ΔH1 + ΔH2 + ΔH3 + ΔH4 + U
27.List the characteristics of Gibbs free energy.

➢ Free energy is defined as G = H – TS
(where G – free energy, H – enthalpy and S – entropy).
➢ G is a state function.
➢ G – Extensive property, ΔG – intensive property.
➢ G has a single value for the thermodynamic state of the system.
Process Spontaneous Non - spontaneous Equilibrium
ΔG – ve +ve zero
V.SURESHKANNA., PG.ASST., G.H.S.S. THIRUMANJOLAI.


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https://material.kalvikadal.

7. Define is Gibb’s free energy.

11. Define Heat of neutralization.

17. State the third law of thermodynamics.

ΔH1 = heat of sublimation of Ca(S)

ΔHf = ΔH1 + ΔH2 + ΔH3 + ΔH4 + ΔH5

20. State the various statements of second law of thermodynamics.

Work involved in expansion processes:-

➢ For a given system with an ideal gas

For reactants (initial state) :

ΔH1 = Heat of sublimation of Na(S)

27.List the characteristics of Gibbs free energy.

V.SURESHKANNA., PG.ASST., G.H.S.S. THIRUMANJOLAI.

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