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Chapter 3

Thermodynamics
MCQs.
1.
Which of the following is the symbolic form of the first law of
thermodynamics?

2.

(A) U = q W

(B) W = U q

(C) U = q + PV

(D) q + W = U

The system in which the property of the system depends on the


quantity of substance, such a property is called?
(A) Specific property

(B) Physical property

(C) Thermal property


3.

(D) Extensive property

For the thermal reaction occurring in nature.


(A) Temperature is always zero

(B) Temperature is always high

(C) Temperature is always low

(D) Temperature can be of any

order
4.

In which condition the relation H = U + PV can be said to be true


for a closed system ?
(A) Constant temperature
(B) Constant pressure
(C) Both constant temperature and pressure together
(D) Constant temperature and volume

5.

For which reaction ~S can be maximum?


(A) Mg(S) +

1
2

O2(g) MgO(S)

(C) C(s) + O2(g) CO2(g)


6.

(B) CaCO3(S) CaO(S) + CO2(g)


(D) N2(g) + O2(g) 2NO(g)

In which of the following entropy decreases ?


(A) Preparing aqueous solution of common salt
(B) Change of water into ice

(C) Dry ice placed in an open vessel


(D) Melting of ice
7.
What change is observed in the isothermal condition of an ideal
gas ?

8.

(A) Decrease in enthalpy

(B) Increase in internal energy

(C) Decrease in internal energy

(D) Enthalpy will be constant

Which relation shows the value of ~S for a reversible reaction?


(A) T - qrew

9.

(B)

qrev
T

(c) qrev + T

For a spontaneous reaction


(A) H = +ve, S = -ve

(b) H = -ve, S = +ve

(C) G = +ve, S = -ve


10.

(C) G = -nFEcell

12.

(d) G = +ve, H = +ve

Which of the following relations is correct for free energy change


and cell potential?
(A) G = nFEcell

11.

(d) qrev T

n
F

(b) G = -

(d) G =

nF
E cell

The reaction A + B C + D is spontaneous in forward direction,


then which signs represent G and S respectively ?
(A) Positive and negative

(B) Positive and positive

(C) Negative and positive

(D) Negative and negative

For an ideal gas, during an adiabatic reaction always,


(A) Decrease in temperature (B) q = 0
(C) W = 0

13.

Ecell

(D) H = 0

Which of the following statements is correct?


(A) G may be less or more or equal to H
(B) G always changes with H

(C) G is always more than H


(D) G is always less than H
14.

What will be the value of G if Kc = 1 for a reaction?


(A) Infinite

15.

(B) 0

(D) Positive

Which law of thermodynamics gives information about definite


entropy of a substance?

(A) First law


Zeroth law
16.

(C) Negative

(B) Second law

(C) Third law

(D)

What is the ideal condition for a reaction occurring on its own?


(A) TS =H, H = +ve S = +ve
(B) TS = H,

H = -ve S = -ve

(C) TS >H, H = +ve S = +ve


(D) TS >H, H = +ve S = -ve
17. The reaction of quick lime with water is reversible at the room
temperature
and at low temperature, therefore,

18.

(A) H and S both +ve

(B) H = +ve and S = -ve

(C) H = -ve and S = +ve

(D) H and S both -ve

Which is the correct relation between G and Kp?


(A) Kp =
(C) Kp = e

19.

e
RT

( )

-G / RT

(B) Kp =

G
RT

(D) Kp = -RT logG

What can be the value of absolute entropy of free element?


(A) Always negative
(C) Always zero

(B) Always positive


(D) Zero at 273 K

20. Which system is indicated by the reaction of cooking rice in a


pressure cooker?
(A) Open system

(B) Closed system

(C) Isolated system

(D) All the systems

Answer:
1.
2.
3.
4.
5.
6.
7.

B
D
D
B
D
B
D

w=V-q
Extensive property
temp. can be of any order
Constant pressure
N2+O2 2NO(g)
Change of water into ice
enthalpy will be constant
qrev
8. B
T
9. B
10.
11.
12.
13.

H = -ve, S = +ve
C
G = -nFEcell
C
negative & positive
B
q=0
A
G may be less (av) more (ov) equal to H

Write the answers of the following question in brief.

Q1.

What is meant by a system?


An extremely small part of the universe which is separated from the
remaining part of universe by a definite boundary and on which we
note the observations of the experiments carried out by external
changes is called system.

Q2.

What an isolated system is called? Give example.


The system which is not able to exchange energy and matter on its
own with surrounding is called an isolated system.
The hot tea poured in a thermos flask of good quality provides its
example at a particular moment, but after some time, it provides
the example of the closed system. Hence, it is difficult to find an
example of an absolute isolate system.

Q3.

What is meant by closed system? Give example.


The system which can exchange energy on its own with surrounding
but the exchange of matter on its own is not possible, is called a
closed system.

For example, the c6ld or hot water poured in the bottle and closed
with a cork.
Q4.

What exothermic and endothermic reactions are called?


A chemical reaction in which energy is released or evolved is called
exothermic reaction. Generally, energy is evolved during the
formation of a chemical bond.
A chemical reaction in which energy is to be supplied is called
endothermic reaction. Generally, energy is to be supplied for
breaking a chemical bond.

Q5.

What extensive property is called?


Some properties of the substance depend on the quantity of the
matter. These properties are known as Extensive properties.
The mass of a substance, volume, enthalpy of formation, entropy,
free energy, elevation in boiling points, depression in freezing point
etc. are such types of properties.

Q6.

What an intensive property is called?


The properties of the substances which do not depend upon the
mass of the substance but depend upon the structure of the
compounds are known as intensive properties.
The melting point of solid substance, density, boiling point of liquid,
conductivity, refraction etc. are such types of properties.

Q7.

What a state function is called?


The values of the properties of the system which depend on the
state of the system, but do not depend on the method, how the
state can be obtained, is called the state function.

Q8.

Give definitions of internal energy and enthalpy.


In every substance definite energy is stored in it on the basis of its
mass and characteristic structure, which is called internal energy
(U).
The total amount of energy obtained from internal energy (U) of
substance and energy obtained by product of pressure (P) and
volume (V) is called enthalpy (H).
H = U + PV

Q9.

Which types of work are observed in chemistry?


In chemistry mainly two types of works are observed: (i) Electrical
work and (ii) Mechanical work.

Q10. Give definition of heat capacity.


The quantity of heat required for increase 111 temperature by 1 C
of any substance is called heat capacity (C) of that substance.
:. Heat Capacity =

Absorbed heat
Differencetemperature

Q11. Give definition of enthalpy of reaction and heat of formation.


When a chemical reaction occurs at constant pressure and constant
temperature, the change in heat is called enthalpy change H or
heat of reaction.
When one mole of compound is formed under standard conditions
from elemental state of constituent elements, thermal change is
called standard enthalpy of formation fH.
Q12. What a thermal equilibrium is called?
When the temperatures of the two substances become the same,
the conduction of heat does not take place in them. This condition
(state) is called thermal equilibrium.
Q13. When is the total heat absorbed by the system during the process
used up in work?
If the internal energy of the system during any process remains
constant, then U = O. i.e., q + W = 0 or q=-w. This indicates that
the total heat absorbed by system during the process is completely
used up in the work.
Q14. Mention the equation of entropy change for the expansion of an
ideal gas in vacuum.
S = R in

V2
V1

= 2.303 R log

V2
V1

Where, V1

= initial volume of gas

Where, V2

= final volume of gas

Q15. Write the formula for the entropy of substances experiencing


sublimation.
S

(sublimation)

H sublimation
T

Q16. The ice cube kept at room temperature melts on its own. Which law
of thermodynamics is obeyed by the reaction?
It obeys the first law of thermodynamics.
Q17. What is meant by temperature of a substance?
The level of thermal energy of a substance is called its temperature.
Q18. The entropy of water vapour is more than that of water. Why?
As the randomness in molecules is more in gaseous state than in
liquid state, the entropy of water vapour is more than that of water.
Q19. What will be the values of G at 270 K and 275 K?
At 270 K = -3c temperature, the ice does not melt on its own,
hence G is positive
At 275 K = 2c temperature, the ice will melt on its own, hence G
is negative.
Q20. Give definition of standard free energy of formation.
The value of change in free energy in direct reaction when 1 mole
compound is produced from its elements in standard state will be
equal to the value of change in standard free energy of formation of
the compound.
Q21. Write the equation showing relation between free energy change
and cell potential.
G = -nFE

ceil

where E ceil is the difference of standard reduction potentials of both


the half cells of the complete cell.
Q22. Why does the value of entropy of a substance increase with increase
in temperature?
With the increase in temperature the translational motion as well as
rotational motion and vibrational motion increase and so there is

increase in randomness at molecular level. Hence the entropy


increases.
Q23. Write limitations of the second law of thermodynamics.
The second law of thermodynamics does not give information about
the rate of chemical reactions.
Q24. Write the third law of thermodynamics.
The value of entropy of a completely pure crystalline substance is
zero at absolute zero temperature.
Q25. Mention the-equation showing the relation between free energy and
change in pressure of all ideal gas.
G

= nRT

In

G = 2.303 nRT In

P1
P2
P1
P2

where n is the number of moles, P 1 and P2 are pressures at initial


and final states.
Q26. What is meant by entropy?
Entropy is the measurement of randomness of the substance.
Q27. By which system the maximum work can be done?
The more negative value of G for any system, the higher the value
of maximum work done by the system.
Q28. What will be the value of equilibrium constant if H< TS at 298 K
temperature.
If H < TS at 298 k, then by G = H TS, the value of G will be
negative.
Q29. What will be the value of oils for ice kept at 275 K and 265 K
temperature?
The value of S for ice at 275 K will be maximum and at 265 K will
be minimum.
Q30. "The value of absolute free energy of any substance cannot be
determined." Why?

The absolute value of free energy of any substance cannot be


determined because it depends on the absolute value of enthalpy of
the substance.
G = H - TS

* Write answers of the following questions:


1.

What is meant by system? Explain giving its types.


An extremely small part of the universe which is separated from the
remaining part of universe by a definite boundary and on which we
note the observations of the experiments carried out by external
changes is called system. (1) Open system (2) Closed system (3)
Isolated system

2.

What is meant by process? Explain its types.


Process: The conversion of state of system from one to another is
called a process.
Types
(1) Isothermal Process: During the change in the system, if the
temperature of the system does not change that is temperature
remains constant, then, the process is called Isothermal process.
(2) Adiabatic Process: During the change in the system, if the
system does not lose heat or does not receive heat, then the
process is called Adiabatic process.
(3) Isobaric Process: If the system contains gaseous materials and
the pressure of the system remains constant during the change,
then that process is called Isobaric process.

3.

Explain extensive and intensive properties.


Extensive Properties: Some properties of the substance depend on
the quantity of the matter. These properties are known as Extensive
properties.
The mass of a substance, volume, enthalpy of formation, entropy,
free energy, elevation in boiling points, depression in freezing point
etc. are such properties.
These properties are expressed in the unit of per (av) mole -1
generally.

Intensive Properties: The properties of the substances which do not


depend upon the mass of the substance but depend upon the
structure of the compounds are known as intensive properties.
The melting point of solid substance, density, boiling point of liquid,
conductivity, refraction etc. are such type of properties.
4.

Explain in detail the state functions.


The values of the properties of the system which depend on the
state of the system but do not depend on the method how the state
can be obtained is called the state function.
For example, there can be different methods to take a substance
having mass (m) to a height (h) but the value of its potential energy
mgh at that height is constant. Thus, potential energy of a
substance is its state function.
In the same way, 1 mole of any ideal gas possesses 22.4 litre
volume at 273 K temperature and I atmosphere (bar) pressure but
the volume does not depend on the state of the substance before
bringing to 1 atmosphere and 273 K.
Thus, the definite volume of a definite quantity of a gas at constant
temperature and pressure is the state function of the gas.
The other state functions of this type are (i) Internal energy (U) of a
substance (ii) Enthalpy (H) of a substance (iii) Entropy (S) of a
substance (iv) Free energy(G) of a substance etc.

5.

Explain internal energy.


In every substance definite energy is stored in it on the basis of its
mass and characteristic structure, which is called internal energy
(U).
This energy is stored in the form of kinetic energy and potential
energy. The component particles of a substance have their linear,
rotation and vibration energy. In addition, their electron and nucleus
also possess different types 0 motion. Hence, substance possesses
kinetic energy.
In the same way, substance possesses potential energy due to
repulsion between electron-electron and repulsive forces between
nucleus-nucleus as well as attractive forces between electron and
nucleus.

Thus, the total energy available from a substance is called internal


energy (U) of the substance.
The value of internal energy of any matter depends on temperature.
If the physical state of substance changes, the internal energy
present in it also change. As the absolute value of internal energy
cannot be measured the change in internal energy can be measured
accurately by experiment.
6.
Write the First law of thermodynamics and give its symbolic
equation.
The total quantity of energy in the universe is constant. Energy can
neither be created nor can be destroyed but transformation of one
form into another form can be possible.
The above statement is known as first law.
- Symbolic eq4
U= q + w
Where

U = change in the internal energy of system.


q = Amount of heat lost (ov) gain by system
w = work done by (ov) work done on the system

7.

Explain the mathematical form of the first law of thermodynamics.


In the symbolic equation of the First law of thermodynamics, when it
is used for the calculation, then, generally, (+) positive and (-)
negative signs are connected with q and W.
(1)If heat is lost during process in the system, the value of q is
negative (-) or the value of exothermic reaction is always
negative (-).
(2)If heat is added during the process in the system, the value of q
is positive (+) or the value of q for endothermic reaction is
always positive (+).
(3)If the work is done on the system, then the value of W is always
positive (+).
(4)If the work is done by the system, then the value of W is always
taken negative (-).
If the internal energy of the system during any process remains
constant then U= O. i.e., q + w = 0 or q=-w. This indicates that the

total heat absorbed by system during the process is completely


used up in the work.
8.

Explain enthalpy and First law of thermodynamics.


The total amount of energy obtained from internal energy (U) of
substance & energy obtained by product of pressure (P) & volume
(V) is called enthalpy (H)
H = U + PV
Hence, if there is a change in state of a system, the change in its
enthalpy can be shown as,
H = U + (PV)
H = U + PV + VP
If the rn occurs at constant pressure, P=0, so H = U + PV
According to first law of thermodynamics, if the r n occurs at constant
pressure, then work done by the system is only of PV type and so
q=qp
W= - PV
V = qp - PV
So H = (qp - PV) + PV
H = qp
Thus, the change in enthalpy of the system in which chemical
reactions occur, at constant pressure is equal to the value of the
heat gained (or) lost by the system.

11.

Deduce the relation between Cp and c,


The heat capacity (cp) for temp change at constant pressure.
CP =

qp
T

& qp = CP x T = H

The heat capacity (CV) for temp change at constant volume,


- for 1 mole ideal gas,
H = U + (PV)
Now PV = nRT
So for 1 mole PV = RT (:: n=1)

H = U + (RT)
H = U + RT
Putting values of H & V from eqn.

1&2

CpT = CvT + RT
Cp =

T (Cv + R)
T

Cp = Cv + R
Cp Cv = R
- Similarly ratio of Cp & Cv is also constant Cp/Cv = r (gamma)
Where r=constant v=1.4 for ideal gas.
10.

Write a short note on heat capacity.


Enthalpy is the state fn. for measuring the changes in heat of the
system at constant pressure. Which is not useful for determining
changes in energy at constant volume. So new function is required
to explain the relation betn. temp & changes in heat at constant
pressure (or) at constant volume and this new function is called heat
capacity.
It is defined as the quantity of heat required for increase in
temperature by 1c of any substance.
It is expressed as CV1 if the temp. of substance is increased by 1c
at constant volume.
It is expressed as Cp, if the temp. of substance is increase by 1c at
constant pressure.
When the initial temperature T1 of a sample of gaseous substance is
changed to temperature T2, then the relation between heat (q), heat
capacity (C) and difference in temperature (T2 - T1) is shown by,
q = C x T2 - T1
q = C x T
C=

q
T

Heat capacity =

Absorbed heat
Differencetemp

Unit of heat capacity is joule/kelvin.


It is proportional to the quantity of the substance & so it is an
extensive property.
Specific Heat Capacity:
The quantity of heat required for increase of temperature of 1 gram
substance by 1 C is called specific heat capacity.

Specific

heat

capacity

Absorbed heat
( Differencetemperature) x(Weight of subs tancein gram)
Unit is joule/kelvin gram
Molar Heat Capacity:
The quantity of heat required for increase of temperature of I mole
substance by 1 C is called molar heat capacity.
Molar heat Capacity =

Absorbed heat
(Differencetemperature) x( Molecular weight)

Unit is joule/kelvin mole


11.

Write the Second law of thermodynamics and in which forms it can


be r expressed?
The Second law of thermodynamics explains in which direction,
either the forward or the reverse, the reaction will spontaneously
occur. It can be expressed as.
(i) In all spontaneous processes, the entropy of the universe
increases.
(ii) The free energy of the system in all the spontaneous processes
decreases.

12.

A system did the work of 785 joule after loss of 525 joule heat find
the chemical change in its internal energy.
The system losses heat

q = -525 joule

The work is done by system

w = -785 joule

So accordingly to first law of thermodynamics, U=q+w = -525-785


= -1310 joule
13.

A system absorbed 650 joules heat & did the work its internal
energy change is 440 joules. Then find the out how much work has
been done.
The system absorbed heat

q = +650 joule

Change in internal energy

U = 440 joule

So accordingly to first law of thermodynamics,


U=q+w
440 - = 650 + w
w = -210 joule
14.

Explain Gibbs free energy and useful work.


Free energy possesses relation with useful work. The change in free
energy associated with any process is the value of maximum
possible work obtained from that process, i.e. free energy is
associated with maximum useful work ie.
G = -W max (-ve value for rn. occurring on their own.)
- The process for which value of G is more negative then max. work
can be done by such process.
- When electrochemical call is in operation the electrical work done
by the cell welect is
G = - w (elect)
- But the electrical work done by
Welect = nFe cell.
coulomb

Where,

F = Faraday constant = 96500


n = Number of electrons passing

Now, G = -w (elect)
G = -nFE cell
It the cell is in standard state & the change in free energy is
associated with reaction & standard electrochemical cell potential,
than the relation between then can be shown by

G = -nFE cell
Potential
15.

Different

of

standard

red.

Explain the standard free energy of formation of a compound.


The standard free energy:
The value of change in free energy in direct reaction when 1 mole
compound is produced from its elements in standard state well be
equal to the value of change in standard free energy of formation of
the compound.
For ex. Water is formed by direct reaction of 1 mole of H 2 & half
mole of O2 at 298k temp. and 1 bar pressure, water is obtained as
liquid then change in free energy of the rn. For,
H2(g) + O2 (g) H2O(l) the value of free energy is 237.13 kJ/mole.
The heat of formation for H2(g) + O2(g) H2O (l)
GfH2O = -237.13 Kj/mole at 298 k because the values of free
energies of H2 & O2 are accepted as zero.
The change in standard free energy of the reaction can be
calculated from the,
G(Reaction) = G(product) - G (reactants)

16. Explain the expansion of an ideal gas in vacuum and change in


entropy.
When a vessel filled with one mole of an ideal gas, connected to an
evacuated vessel, there is no work done by the system during
expansion of the gas on its own, because expansion of the gas on its
own, because w=PV & P=zero because of vaccum.
In addition to this the gas does not loss (or) gives the heat in this
process. So q=0 and
U = q + w
=0+0
U = 0
This process is not reversible. Hence qirr = 0. This in the expansion
of an ideal gas in vaccum, P=0, U=0 & qirr = 0.
As the volume of the gas increase during the reversible process, the
change in entry will be there.

We know for 1 mole of gas,


V2
V1

qrev = RT ln

qrev
T

= RT ln

V2
V 1 = 2.303 R log

S = R ln

qrev
T

V2
V1
V2
V1

= S

Where V1 = initial volume of gas &


V2 = final volume of gas.
Acco. To bolees law,
P1 V 1 = P2 V 2

V2
V1

P1
P2

Where P1 = initial pressure of gas


P2 = final pressure of gas

S = R ln

P1
P2

S = 2.303 R log
17.

P1
P2

Explain the Third law of thermodynamics.


Generally, the value of entropy of a substance increases with
increase in temperature, because, the randomness increases with
increase in temperature.
The value of entropy increases because there is increase in their
oscillation motion, linear motion and rotation as against to this, with
decrease in temperature, the oscillation motion, linear motion and
rotation motion of the molecules of substance decrease and so

randomness decrease and decrease 111 randomness decrease the


value of entropy.
German scientist Nernst expressed, in 1906, that the value of
entropy of a completely pure crystalline substance decreases with
decrease in temperature. On the basis of this, the third law of
thermodynamics can be expressed as below:
"The value of entropy of a completely pure crystalline substance is
zero at absolute zero temperature"
i.e. the arrangement of component particles of an absolutely pure
crystalline substance is completely systematic at absolute zero
temperature. Hence, entropy is least in solid, more in liquid and
highest is gas.
18.

Give limitations of the First law of thermodynamics.


(1) On the basis of first law of thermodynamics it is not possible to
know whether any chemical reaction will occur on its own
(spontaneous)
(2) The reactants will be transformed to what proportion of products
also cannot be obtained from the first law of thermodynamics.

19.

Discuss characteristics of the reactions occurring on their own.


The hot tea taken in a saucer or water taken in a vessel; gets cold
on its own but for how long? It is found from the general experience
that when its temperature becomes equal to that of the
surrounding, it stops decreasing. This way hot water goes on losing
the heat until thermal equilibrium between water and surrounding
does not establish. In the same way the gas filled in a bulb tries to
diffuse to the bulb being evacuated till the pressure in both the
bulbs become equal. This is also a type of pressure equilibrium
condition.
All the chemical reactions continue spontaneously till the
equilibrium condition is not established and when equilibrium state
is established the concentrations of reactants and products remain
constant. If we understand this statement in other way, then it can
be said that the spontaneous reactions occur in the direction of
establishing equilibrium between reactants and products. When
equilibrium is established the reaction is also balanced. Thus,
reaction attains equilibrium while going from reactants to products
or from products to reactants.

20.

What is meant by entropy? Explain using the concept of entropy,


how the direction of a reaction to occur on its own is determined.
Entropy is the measurement of randomness of the substance.
To determine whether a reaction will occur spontaneously or not, the
calculation of change in entropy of the system and the surrounding,
assuming that the reaction will occur of S system and S
surrounding is carried out.
If the sum of these two values is positive (+ve), then the forward
reaction will occur spontaneously and if the sum of these two values
is negative (-ve), then the reverse reaction will occur spontaneously
and if the sum of these two values is zero, then reaction will be in
equilibrium.
S system + S surrounding > 0, the reaction will occur on its own
(Spontaneous reaction.)
S system + S surrounding < 0, the reaction not occur on its own (NonSpontaneous reaction.)
S system + S surrounding = 0, the reaction will remain in equilibrium
(Equilibrium reaction)

* Long questions
1.
Explain internal energy and enthalpy and deduce the relation
between them.
* Internal Energy (U):
In every substance definite energy is stored in its on the basis of its
mass & characteristic structure, which is called internal energy.
It is stored in the form of kinetic energy & potential energy. The
compound particles of a substance have their linear rotation and
vibration energy. Their electron & nucleus also possess different
types of motion. So substance possesses kinetic energy.
Substance also-possesses potential energy due to repulsion
between electron-electron & repulsive forces between nucleusnucleus as well as attractive forces between electron & nucleus.

Thus, the total energy available from a substance is called internal


energy (U) of the substance.
The value of internal energy depends on temp. if physical state of
matter changes the internal energy also changes.
During
energy
energy
energy

a chemical rn. Internal energy of products (UP) & internal


of reactants(Ut). The energy difference is equal to internal
of product & reactants. It is expressed as change in internal
(V).

During any reaction. If these is change in the volume of the matter,


there will be change in its work. When any chemical r n. is carried out
at constant volume, internal energy of reactant & product.
So qv = Up Ur = U
* Enthalpy:
The total amount of energy obtained from internal energy (U) of
substance and energy obtained by product of pressure (P) and
volume (V) is called enthalpy (H).
H = U + PV
If any reaction is carried out in an open vessel, then the reaction
system is in direct contact with the atmosphere and so the pressure
of constant atmosphere applies. Thus, any chemical reaction, when
carried out at constant pressure, then the change in its energy is
called enthalpy change (H)
qp = Hp - Hr = H
Where HP = enthalpy of products
Hr = Enthalpy of reactant
2.

Write the First law of thermodynamics and explain it in detail in the


symbolic equation and in the mathematical form.
* First law of thermodynamics:
The total quantity of energy in the universe is constant. Energy can
neither be created nor can be destroyed but transformation of one
form into another form can be possible.
* Symbolic equations:

Suppose, the internal energy of any system, at a definite equilibrium


state is U1. If this system after undergoing a reaction attains a new
equilibrium state having internal energy U2 then the heat absorbed
by the system (or) heat lost by the system during this rn is q.
Now, if the work done (W) is on the system or the work done by the
system is W, then according to First law of thermodynamics,
U2 = U1 + q + w
U2 U1 = q + w
U = q + w
This eqn. is the symbolic form of first law of thermodynamics.
* Mathematical form of first law of thermodynamics.
1. If heat is lost during the system, q = -ve (or) the value of
exothermic rn. is always negative -ve.
2. If heat is added during the process in the system, the value of q is
positive (+) or the value of q for endothermic rn. is always positive
(+ve).
3. If the work is done on the system, then the value of W is always
positive (+ve).
4. If the work is done by the system, then the value of W is always
taken negative (-ve).
- If the internal energy of the system during any process remains
constant then U = O. i.e., q + W = 0 or q=-w. This indicates that
the total heat absorbed by system during the process is completely
used up in the work.
3.

Explain enthalpy of reaction, enthalpy of neutralization & enthalpy


of formation.
When a chemical reaction occurs at constant pressure and constant
temperature, the change in heat is called enthalpy change H or
heat of reaction.
To understand the characteristics of the reaction heat expressed as
standard enthalpy change (H). The element (or) compound whose
solid, liquid, (or) gaseous form is stable at 1 bar pressure and 298K
temp, it is called a standard state.

Solid elements sodium, copper, silver etc are accepted as standard


states. The gaseous elements like H1, N1, O1, and C1 are taken in the
form of their diatomic molecules H2, N2, O2 and Cl2 respectively as
standard state.
The elements which are available in allotropic forms, their most
stable allotrope is considered as standard state, ex., graphite which
is allotrope of carbon & rhombic sulphur allotrope in standard form.
The value of standard enthalpy (H) of any element is considered as
zero. Starting from the standard forms of the reactants and bringing
the products obtained at the end of chemical reaction in standard
state, the value of total change in the enthalpy during the reaction
is called standard enthalpy change of the reaction (H). This
standard enthalpy change is called "Heat of reaction". Its value is
expressed in kilojoule.
* Enthalpy of neutralization:
Experimently when 1 mole dilute aqueous solutions of strong acids
HCI, H2SO4 or HNO3 are neutralised by 1 mole of strong base like
NaOH (or) KOH, one mole of salt and one mole water are produced,
with 56 kilojoule heat is produced which is known as enthalpy of
neutralization.
When one equivalent weight of any strong base in its dilute solution
neutralises one equivalent weight of any strong acid in its dilute
solution, the heat produced is called enthalpy of neutralisation.
The standard enthalpy of neutralisation is constant equal to 56
kilojoule/mole.
H+(aq) + OH-(aq) H2O(l)

H = -56 KJ/mole

In neutralisation reaction between acid and base the net reaction is


the formation of H2O(l) by reaction of H+ of acid & OH- of the base,
hence, standard enthalpy change in the rn. between these two ions
is called standard enthalpy of neutralisation.
* Enthalpy of formation fH:
When one mole of compound is formed under standard conditions
from elemental state of constituent elements, thermal changes is
called standard enthalpy of formation fH.

Generally, the value of enthalpy of formation of stable compounds is


negative
(-ve) but in certain stable compounds the value of heat
of formation is positive (+ve).
C(s) + 02(g) CO2(g)
fH = -393.5 KJ/mole
In the formation of carbon dioxide C0 2 by combustion of carbon, the
standard enthalpy change will be
fH = -393.5 KJ/mole
fH = Hp - Hr = (Total enthalpy of products)
- (Total enthalpy of reactants)
= (Standard enthalpy of CO2(g))
- (Standard enthalpy of C and O2)
Here C & O2 are in standard state, so their enthalpies are
considered as zero.
fH = (Standard enthalpy of CO2(g))
= fH CO2 = enthalpy of formation
enthalpy of information fH CO2 = -393.5 KJ/mole
Here H = (-ve) so the reaction is exothermic, Thus, the total
enthalpy of products, is less than the total enthalpy of the reactants.
4.

Write the Hells law of constant heat summation & explain giving
example. Mention its uses also.
Acco. Too Hesss law, "The total change in enthalpy in a chemical
reaction is equal to the algebraic sum of the changes in enthalpy
occurring during different steps."
This law can be explained on the basis of the first law of
thermodynamics.
The change in enthalpy at constant pressure and constant temp in a
chemical reaction is equal to the change in enthalpy H of that
reaction.
The enthalpy of reactants and products are constant at constant
pressure and constant tem. Hence, if the reaction occurs in one step

or more steps even then the value of enthalpy change remains


constant.
It is apparent from this, that if a chemical reaction occurs in different
steps, the total change in enthalpy is equal to the algebraic sum of
enthalpy changes of different steps.
The important outcome of Hesss law is that of the addition (or)
subtraction of thermochemical eqn. can be carried followed by
addition (or) subtraction of corresponding changes.
As q result, the enthalpy changes, which cannot be measured
experimently can be made possible on the basis of calculating the
enthalpy change according to Hesss law.
The enthalpy evolved (or) absorbed during different chemical
reactions like enthalpy of formation, enthalpy of combustion,
enthalpy of neutralization etc. can be determined on the basis of
Hesss law.
For ex. Co2 is formed by chemical rn. between carbon & oxygen. This
reaction can occur in the following steps.
(a) C(s) + O(g) Co2(g)
(b)(i) C(s) + O2(g) CO(g)
(ii) Co(g) + O2(g) Co2(g)

H = -393.5 KJ/mole
H(i) = -110.5 KJ/mole
H(ii) = -282.96 KJ/mole

H(i) + H(ii) = H = -393.5 KJ/mole


In reaction (a) direct combustion of carbon takes place in one step.
While reaction (b) takes place in two steps, when first step (i) and
second step (ii) are added, the value of H will be equal to the value
of H in reaction (a).
5.

Write the second law of thermodynamics & explain entropy.


The second law of thermodynamics explains in which direction,
either the forward (or) the reverse, the reaction will occur
spontaneously.
(i) In all spontaneous processes, the entropy of the universe
increases.
(ii) The free energy of the system in all the spontaneous process
decreases.
Ex. Of spontaneous reaction.

(a) If two substances having different temp are kept in contact with
each other, the heat will always spontaneously flow from higher
temp to lower temp.
(b) Water always flows from higher level to lower level.
* Entropy:
Entropy is the measurement of randomness of the substance. To
understand consider following ex.
Suppose four squares of the size 1x1 and are drawn on a paper &
one honeybee flies over it.
1
2
1
2
3
3
4
4
5
6
7
8
9
Maximum & numbers 1, 2, 3, 4 will be required to show position of a
honeybee. Now, this honeybee flies over nine squares on the second
paper.
Maximum nine number 1 to 9 will be required to show the position
of the honeybee. Thus, more co-ordinates are required to show the
position of a honeybee.
So it can be said that if the honeybee flies & sits on the second
paper then, its entropy wile increases. The measurement of entropy
of any system is the measure of randomness of the system.
The entropy of crystalline solid substance is least because the
arrangement of molecules is systematic in crystalline solid.
While entropy of liquid substance is more than solid because of
randomness of molecule is more. Same way entropy of gaseous
substance is maximum, because the randomness of molecules in
the gas is maximum.
6.

What is free energy? What is the relation between changes in free


energy during a chemical rn & the change in entropy? On the basis
of this explain under which conditions the reaction will occur on its
own,
* Free energy:
To know whether a chemical reaction will occur on its own (or) not
can be decided on the basis of the determination of entropy of both
the system & surrounding.

Free energy is such a state function that in determining, whether


reaction will occur on its own (or) not, only the change in free
energy of the system is to be found out.
The relation of this-state function free energy (G) with enthalpy (H)
of the system & the entropy (S) of the system can be shown by
following equation.
G = H TS
But, if the state of the system changes at constant temperature,
there are changes in the values of all the three state functions which
can be shown as below,
G = H - TS
Where H & S are the values of change in enthalpy & change in
entropy with the help of this G can be obtained.
For a reaction occurring on its own (spontaneous) the value of G
obtained is negative because there is decrease in free energy of all
the reactions in the system.
For reactions not occurring on their own (non-spontaneous), the
value of G will be positive (+ve) & G becomes zero (O) in reaction
in equilibrium.

* Solve the following examples:


1.

The change in internal energy of a given reaction at 300 K is -908


kjoule mole-1, then calculate its enthalpy change.
4NH3(g) + 5O2(g) 6H2O(l) + 4NO(g)
U = -908 KJ/mole
T = 300 k
= 8.314 x 10-3 KJ

R = 8.314 J.
n (g)

= np(g) n r (g)

= 4 (4+5)
= -5
H

= U + n(g) RT

= -908 + (-5 x 8.314 x 10-3 x 300)


= -908 12.47
= -920.47 KJ
2.

The enthalpies of formation of CO(g), CO2(g), N2O(g) and N2O4(g) are -110
, -393.81, 82 and 9.7 kjoule mole -1, respectively. Calculate fH for
the following reaction: N2O4(g) + 3CO(g) 7 N2O(g) + 3CO2(g)
fH

= formation enthalpy of products forn enthalpy or react


= (HN2O + 3HCO2) (HH2O4 + 3HCO)
= [82 + 3 (-393.81)] [9.7 + 3(-110)]
= (-1099.43) (-320.3)
= -1099.43 + 320.3
= -779.13 KJ/mole

3.

On the basis of the following equations, calculate the standard


enthalpy of formation of CH3OH(i).
CH3OH(l) +

3
2

O2(g) CO2(g) + 2H2O(l) fH = - 726 kjoule mole-1

C (Graphite) + O2(g) CO2(g) fH = - 393 kjoule mole-1


H2(g) +

1
-1
2 O2(g) H2O(l) fH = - 286 kjoule mole

For CH2OH the eqn for std. enthalpy of formation is


C(s) + 2H2(g) +

1
2

O2(g) CH3OH(2)

Now, reverse eqn. (1) multiply eqn. (3) by 2 and add eq n. (1) + eqn.
(2) + eqn. (3)
CO2(g) 2H2O(l) CH3OH(l)
C(graphite) + O2(g) CO2(g)
2H2(g) + O2(g)

2H2O(l)

3
2 O2

fH = +726 KJ/mole
fH = -393 KJ/mole
fH = -572 KJ/mole

C(graphite) + 2H2(g) +
4.

1
2

O2(g) CH3OH

fH = -239 KJ/mole

If H = 400 kjoule mole-1 and S = 0.2 kjoule K-1 mole-1 for a


reaction 2x + y z, at what minimum temperature the rection will
be spontaneous ?
2x + y 2
If G = 0

than the rn is in eqn state

G = H - TS
0 = 400 T x 0.2
-0.2 T = -400
T=

400
0.2

= 2000K

i.e. at T=2000K G=0. So at temp T> 2000K G<0


rn occurs spontaneously
5.

For the following reaction, 2P(g) + Q(g) 2R(g) U = -10.5 kjoule and
S = -44.2 joulekelvin-1 Find G for the reaction. Will the reaction
occur on its own? Why?
2P + Q 2R
n(g)

= np(r) n r (g)
= 2 (2+1)
= -1

= U + n(g) RT
= -10.5 + (c-1 x 8.314 x 10-3 x 298)
= -10.5 2.477
= -12.977 KJ.

FG = H - TS
= -12.977 (298) (-44.2 x 10-3)
= 12.977 + 13.17

= 0.193 KJ/m
Here fG = +ve
rn will be not happen spontaneously.
6.

From the given data mention which of the following reaction will
occur on their own at 298 K.
Reaction: X : H = -52 kjoule; S = 956 joulekelvin-1
Reaction: Y : H = -60 kjoule; S = -65 joulekelvirr-1
x, y
for x G = H - TS
= -52 (298) (958 x 10-3)
= -52 285.4
= -337.4 KJ/m
G = -ve
It is spontaneous rn.
For y G = H - TS
= -60 (298) (-65 x 10-3)
= -60 (-19.5)
= -40.7 KJ/m
G = -ve spontaneous.

7.

The changes in enthalpy and entropy for a raction P + Q R + S at


320 Kelvin temperature are 170 kilojoule and 26 joule Kelvin -1. Will
this reaction
be spontaneous? Why ? Find out.
P +qR+S
G

= H - TS
= 170 (320) (26x10-3)
= 170 8.32
= 161.68 KJ/m

= +ve

not spontaneous

8.

Find out the equilibrium constant of the following given reaction at


298 K temperature NO(g) +

1
2

O2(g) NO2(g). The values of fG for

NO and NO2 are 104.2 and 51.3 kjoule mole -1 respectively of 298 K
temperature.
No2(g) + O2(g) No2(g)
G

= GP - GR
= 51.3 - (104.2)
= -52.9 KJ

= -2.303 x RT log K

log K

=
Log k

52.9
2.308 x 8.314 x 1 03 x 298
= 9.2723

= 1.87x109

K
9.

G
2.303 x RT

Find the change in standard free energy of formation and


equilibrium constant of the reaction Fe(s) + Cu 2+(aq)

Fe

2+( aq) + CU(s). The standard electrochemical cell potential is O.


78 volt and F = 96500 coulombs.
Fe + Cu+2 Fe+2 + Cu(s)
Change in ele = n=2
G

= -nFE cell
= -2 x 96500 x 0.78
= -150540 J ( volt x couble = J)

Now, 4.184 J = 1 calorie


-150540 = ?

150540
4.184

G = -2.303 RT log k
-35979.9 = -2.303 x 1.987 x 298 x log k
35779.9
2.303 x 1.987 x 298

log k =

= 26.3859

K = Anti (26.3859)
K = 2.432 x 1026
10.

The value of change in free energy for the following cell reaction at
298 K temperature is -76322 calories. Calculate the potential of the
electrochemical cell. F = 96500 coulomb, 1 Calorie = 4.184 joule.
Reaction: A(s) + B 2+( aq)

A 2+( aq)

+ B(s)

A + B+2 A+2+ B
G
E

= nFE
=

4
nF

1 calorie = 4.184 J
-76322C = ?
- 319331.2 J
E =

319331.2
2 x 96500

E = 1.65 v
11.

The equilibrium constant of the following given reaction is Kp = 2.4


X 10-5 at 298 K temperature.
Reaction : PCI5(g) PCI3(g) + CI2(g) Calculate the value of fG for the
given reaction.
PCl5 PCl3
G

= -2.303 x RT log Kp

= -2.303 x 8.314 x 10-3 x 298 x log (2.4 x 10-5)


= -2.303 x 8.314 x 10-3 x 298 (5.38021)
= -2.303 x 8.314 x 10-3 x 298 (-4.6198)
= 26.3598 KJ.