DISHA SCIENCE ACADEMY

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CHEMICAL THERMO DYNAMICS
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m
ADDITIONAL POINTS FOR SYNOPSIS:
System: • It is a state function and its absolute value can’t
be determined.

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A specific portion of matter under study which
Change in intenal energy can be determined with
is isolated from the rest of the universe with a
help of Bomb Calorimeter.
bounding surface is called a system’s surround-
It depends upon quantity of a substance, its
ings. The rest of the universes which might be in
chemical nature, temperature, pressure and

ot
a position to exchange energy and matter with
volume of the substance.
the system is called the surroundings. For a given system, E is directly proportional to

sp
Types of Systems its absolute temperature.
a) A system which can exchange mass as well as At constant volume, the quantity of heat sup-
energy with the surroundings is called “ open plied to a system (isochoric process) is equal to

g
system”. e.g. lime kiln, ice in an open beaker. the increase in this internal energy, i.e.,
b) A system that can exchange energy with the

surrounding and not mass is called a ‘closed
system i.e., ice in a closed beaker.
c) A system which can exchange neither mass
nor energy with the surroundings is called
blo
.
. In the adiabatic expansion of a gas, it gets cooled
because of decrease in internal energy
In a reversible process, the change in internal

ss.
isolated system e.g., ice in a thermous flask. energy is zero, since E is a state function.
For exothermic reactions, the sign is positive
Extensive Property
ce i.e., .
A property which depends upon the amount of
the substance(s) present in the system, e.g., • In endothermic process while for exo-
mass, volume, energy, work, internal energy, thermic processes.
c
enthalpy, entropy, etc. •Q =
> ∆EERP
v =
dT
dQ 0
EThermodynamic Process:
su

P
R
Intesnsive Property • The operation by which a thermodynamic sys-
A property which is independent upon the tem change from one state to another is called a
amount of the substance(s) present in the sys-
to

thermodynamic process which is always

tem is called ‘intensive property’ e.g., tempera- accompained by change in energy although in
ture, pressure, density, concentration, viscos- case of open system, change of matter may also
are

ity, refractive index, surface tension, specific occur.

heat, etc., (i) Isothermal process:
State Function A process in which although heat enters or
The thermodynamic parameters which depend
sd

leaves the system yet temperature of system re-

only upon initial and final states of the system mains constant throughout the process.
and are independent of how the change is ac-
In this change of state (e.g. freezing, melting,
aim

complished are called state functions. evaporation, condensation) is an isothermal

Example:
Internal energy, enthalpy, entropy, free energy,
pressure, temperature, volume, etc. Work and
heat energy are not state functions.
w.
process, Isothermal processes are often car-
ried out by placing the system in a thermo state
(a constant temperature bath)

(ii) Adiabatic process:

Internal Energy (E): A process during which no heat enters or leaves
The total energy stored in a substance by virtue of the system during any step of the process, so
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its chemical nature is called its internal energy,i.e.,
it is the sum of its translational, vibrational, rota-
tional, chemical bond energy, electronic energy,
nuclear energy of constituent atoms as potential
energy due to interaction with neighbouring mol-
ecules is called Internal or Intrinsic Energy:
E = Et + Er + Ev + Ee + En + EPE
that temperature will decrease or increase when
the reaction is endothermic and exothermic re-
spectively.
Such process are often carried out in closed
insulated containers such as thermous bottle. for
this change in heat

CHEMICAL THERMODYNAMICS & ENERGETICS

 DISHA SCIENCE ACADEMY
(iii) Isobaric process:
A process during which pressure of the system
remains constant throughout the reaction e.g.,
heating of water to its boiling point and its
vaporisation take place at the same atmospheric
Laws of Thermodynamics:
First law of Thermodunamics: It is simply the
law of conservation of energy which states that
“ Energy can neither be created nor destroyed

m
although it can be converted from one form to
pressure. Expansion of gas in a system is an another”.
example of it. When work is done by the system

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(vi) Isochoric process:
Volume of the system remains constant through- When work is done on the system
out the reaction in such process. The heating of

ot
a substance in non-expanded chamber or In case of small changes
change taking place in a closed system are ex-
(In case work is done by the
amples of these process. In such cases

sp
(v) Cyclic process: system i.e., expansion) or
A process during which system comes to its ini- (in case work is done on the

g
tial state through a number of different pro- system compression) =
cesses, is called a cyclic process, , In (i)

blo
When , i.e., cyclic process,
such cases, .
(ii) When volume remains constant where
Nature of Work and Heat: Work (W) =
v indicates constant volume
, where

ss.
intensity factor is a measure of force respon- (iii) For adiabatic process, ,
sible for work and capacity factor is a measure where q indicates constant heat.
of extent for which work is done (iv) When a gas expands against an external pres-
ce
Thus, sure P, the work done by it will be:
a) Mechanical Work = , i.e., W = − P∆V
c
= × (v) When a gas is compressed, work is done on
δ•Q
∴∆
W
V ∆ ∆×=E
F2Q
dP
dV
dE
P
mgE
V =
< +
=dW
>V=
∆
×
Intensity
Force Q 0V 0hδ1PdV
=−(V ∆
==−
P×Q (+
+∆− WδPdV
−∆
+
−
1∆vV = 2 − V1 )
0Q WQ × Capacity factor
=W)−ve
displacement
factor
V
nFE V
b)Electrical Work = Prrential difference dH V ve
su

the system and is given by

Charge flown = (vi) When a gas expands into vaccum, work done
c)Expansion work = Pressure Change in by it is zero, since P = 0, there fore W = 0.
to

volume = (vii) In case of expansion of a gas, maximum work is

d) Gravitational work = Gravitational force done, if the process is isothermal and reversible.
are

Limitations of First Law of the Thermodynamics:

Height = Units of work = dyne
(i) It does not predict whether the process can
cm or erg (CGS system) Netwon m (Nm)
occur spontaneously or not i.e., whether it is
or Joule (MKS system)
feassiable or not and if so, in which direction. The
i)Work, Heat and Energy have same units
sd

first law does not indicate whether heat can flow

ii)Work is not a state function because amount
from a colder end to a hotter end or not. All that
of work performed depends upon the path
the first law tells that, if the process occurs, the
followed
aim

heat energy gained by one end would be exactly

iii)Positive value of work signifies that the work
equal to that lost by the other end. Similarly, the
has been done on the system by the surround-
first law does not tell whether a gas can diffuse
ings and it leads to an increase in the internal
from low pressure to high pressure or not, whether
energy of the system. Negative value of work
water can run up hill or not, etc.,
w.

indicates that work has been done by the

(ii) The first law states that energy of one form can
system and it leads to decrease in the inter-
be converted into an equivalent amount of en-
nal energy of the system.
ergy of another form. However, by experience,
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iv)The general expression for all type of PV-

it has been observed that although various forms
work can be written as . Thus of enrgy can be completely transformed into
for expansion, i.e., when , is another, heat energy cannot be completely con-
positive. Hence . For verted into equivalent amount of work without
producing some change elsewhere.
compression, , is negative hence
=
CHEMICAL THERMODYNAMICS & ENERGETICS
 DISHA SCIENCE ACADEMY
Second Law of Thermodynamics:
This states that “heat cannot itself pass from a colder
to a warmer body. “Thus, if heat is to be
transferred from the cold to the hot body, work
must be provided by an external agency.. An
alternative and useful expression of the second law
is “ any system of its own accord will always
undergo change in such a way as to increase the
entropy”. “Every perfect machine working
reversibly between the same temperature of source
and sink have the same efficiency whatever be
nature of substance used” (Carnot-theorm)
Lord Kelvin Statement:
“ It is impossible to take heat from a hotter
revervoir and convert it completely into work
by a cyclic process without transferring a part
of it to a cooler reservoir”. This statement rec-
ognizes the fact that the heat engine can never
be 100% efficient
Clausius Statement:
“ It is impossible for a cyclic proces to transfer
heat from a system at a lower temperature to one
at higher temperature without applying some
work”. i.e., without converting some work to heat.
Third Law of Thermodynamics”
This states that for a perfect crystal at about
c
zero on the Kelvin scale, the entropy is zero. “
su
This follows, the predictions of Einstein that the
specific heats of all susbtances would approach
zero at 0 Kelvin and the conclusion of Planck
to
that the entropy of all pure solids and liquids
approach zero at this tempeature.
Spontaneous, Natural (OR) Irreversible Process:
are
“ A process which proceeds of its own accord
without the help of any external agency, is called
a spontaneous process.
sd
“ All natural processes are spontaneous, hence
the term, natural is also used for the spontane-
ous process, also spontaneous processes can-
aim
not be reversed without the help of an external
energy, these are also said to be irreversible.
The term ‘non-spontaneous’ is applied to pro-
cesses which has not natural tendency or urge
to occur, e.g. electrolysis of water. The term
w.
spontaneous does not give any idea of the rate
of the process.
Examples:
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(i) Water flows down-hills spontaneously and the
direction cannot be reversed unless some ex-
ternal work is done on it.
(ii) Heat flows spontaneously from the hot end of a
metallic bar to its cold end but never from cold
end to hot end.
CHEMICAL THERMODYNAMICS & ENERGETICS
(iii) Heat flows spontaneously from a hot reservior to
a cold reservoir. However, transference of heat
from a cold reservoir to hot reservoir as in a re-
frigerator need energy from outside the system.
(iv) Diffusion of a solute from a concentrated solu-
m
tion to a less concentrated solution, when these
are in contact with each other, occur spontane-
.co
ously till the equilibrium is achieved.
(v) electricity flows spontaneously from a point. The
direction of flow can be reversed only when an
external field is applied in the opposite direction.
ot
(vi) A gas expands spontaneosly from a region of high
pressure to a region of low pressure. The reverse
process cannot occur unless work is done on it.
sp
(vii) A piece of zinc dissolution occurs spontaneously
in copper sulphate solution, precipitating cop-
g
per and evolving some heat.
Entropy (S)
blo
It is a thermodynamic quantity which is a mea-
sure of the degree of disorder within any sys-
tem. The greater the degree disorder, the higher
the entropy.
ss.
Thus, for a given substance,
ce
Any change taking place which results in an in-
crease in entropy has a positive entropy change
( ∆S ). Most spontaneous thermodynamic pro-
•(∆
S∆gas
GG 0=
>
) ∆
0
S
SuniverseH > −0T>are
cesses ∆SSsolid
accompained by an increase in entropy.
T liquid
Entropy has units of joules per degree per mole.
The entropy of the universe always increase in
the course of every natural change i.e.,
and energy of universe is con-
served while entropy of universe always in-
creases in any natural or spontaneous process
Gibb’s Free Energy ( )
It is a thermodynamic state function represented
by G (after Willard Gibbs). the free energy
change in any system is related to the
enthalpy and entropy changes by the equation:
is a measure of the maxi-
mum amount of useful work which may be ob-
tained from the change under consideration.
In any system, the value of the free energy
change determines the position of equilibrium
in that equilibirum the free energy . For
substances in their standard state, i.e., 1 mole
at 1 atmopsheric pressure and a specified tem-
perature, the change in free energy is called the
standard free energy change .
This latter quantity is of considerable importance,
in that, it determines the thermodynamic feasi-
bility of a reaction.
 DISHA SCIENCE ACADEMY
For a reaction to be thermodynamically feasible
and this for more products than reactants to be
formed at equailibrium, the value of must
be negative, i.e., there must be a decrease on
standard free energy from reactants to prod-
The specific heat capacity is denoted by c and
can be calculated with the help of formula
where, q = heat requred to raise the tempera-
ture by one degree

m
ucts. and are usually expressed in c = specific heat capacity m =mass
kilojoule per mole for chemical reactions. = temperature chagne

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(i) For spontaneous process, is negative For gases two molar heats viz, molar heat at
(ii) For process in equilibirum, is zero constant pressure and molar heat at con-
(iii) For process occuring in backward direction and stant volume are defined . is always

ot
not in forward direction is positive Stan-
dard free energy change ( ) and equilibirum greater than and both of them are related as

sp
constant are related as below: where R = 2 cal
Where ∆G 0 = Note:

g
(Free energy of formation of products - Free From the ratio of and we get the idea of
energy of formation of reactants) Standard atomicity of a gas.

blo
enthalpies of formation , standard free (a) For monoatomic gas ; Cv = 3 cal
energies of formation (∆G 0f ) and absolute en- Cp 5
tropies of selected substances at 298 K are hence, γ= = = 1.67

ss.
Cv 3
given below:
• The quantity of heat required to raise the tem- (b) For diatomic gas C p = 7 cal ; Cv = 5 cal
perature of a system of one degree is called heat
ce
Cp 7
capacity of that system. This is denoted by hence, γ= = = 1.40

)0U K C p = 8 cal ; Cv = 6 cal

Cv 5
(Heat capacity when volume is constant) and
c

 ∆∆TT vp =T γ = 8 = 1.33

•C
(∆ (c) )0)c=0f∆
=p==−= =×
∆ For
=H×R∆
triatomic
∆TH gas
(Heat capacity when pressure is constant) ∆
qdq
C tG
U
HpvH C 5 ∆
c∆
H−
m
cal
U2.303 ∆ H
RTfusion
log
su

C ∆
vpvP
=
p =  =
6
vaporisation
vS
Thus, in general we can say dT melting
vaporisation
hence, m Tb
to

Heat capacity = • If an ideal gas expands in vacuum adiabatically,

For solids and lquids there is not much differ- no cooling is produced in the process i.e.,
are

. However if a real gas is allowed to

ence between the values of and . How-
expand through a porous plug into the region of
ever for gases these quntities differ which can lower pressure, the gas is cooled and the extent
be calculated as of cooling is proportional to the difference in
sd

pressures of two sides. This phenomenon of

as at constant volume cooling of gas is called Joule-Thomson effect.
This effect is observed when i.e., at
aim

constant enthalpy. The effect is also called Joule-

Similarly as at constant pressure Kelvin effect.
w.

The heat capacity of a substance is directly pro-

portional to the amount of substance i.e., de-
pends upon amount of substance Where, Tm = melting point of substance
ww

In chemical calculations we often use specific

heat capacity and molar heat capacities of which
specific heat is defined as “ The heat required
to raise the temperature of one unit mass by
one degree (either celcius or kelvin)”. When the Where, Tb = boiling point of substance simi-
above definition is given in terms of mole it is larly
considered as molar heat capacities i.e., the heat
capacity of 1 mole of a substance.
CHEMICAL THERMODYNAMICS & ENERGETICS
 DISHA SCIENCE ACADEMY
6. The molar heat capacity of water in equilib-
rium with ice at constant pressure is:

d. 40.45kJK −1mol −1
a. Negative b. Zero
Where, Tsub = sublimation temperature c. Infinity

m
Note
7. The additivity property of (formation)
(i) have (+) ve value for spontaneous processes
value is known as
(ii) have (-) ve value for non-spontaneous process

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a. Kirchhoff’s law
(iii) The zero value of indicates equilibrium state.
b. The Lavosier and laplace law
(iv) For a reversible process at equilibrium can c. Hess’s law d. The pauling law

ot
8. For a reversible process, the total change in
be calculated by , Where qrev = heat
entropy of the universe is equal to
supplied at temperature T in a reversible process a. ∆S (system) +

sp
(surroundings)
Free Energy and Electromotive Force (E.M.F)
of a Cell Using, b. (system) - (surroundings)

g
c. Zero d. Negative
9. Which of the follwoing statements are correct?
∆G = −nFECell

blo
a. The entropy of an isolated system increase

+ 2.303 RT log Q
We have
0
in an irreversible process
− nFECell = − nFECell
2.303 RT
b. The entropy of an isolated system remains
0
log Q

ss.
unchanged in a reversible process
Ecell = Ecell − c. The entropy can never decrease
nF
d. All of the above
ce
LEVEL-I 10. In the following table, which are correct?
1. When heat is supplied to an ideal gas in an iso-

0 H
+ 2.303 logof Q
thermal process, the
0 0 0
Nature Reaction
c
a) Gas will do positive work •∆
1 ≠
H
HHSG −2GnFE
==q∆rev ∆H sublimation
∆SSsublimation
∆ RT
=
su

Spontaneous at all
b) Gas will do negative work = cell

-ve +ve -ve

temparature
c) Kinetic energy of gas will increase T Tsub

Non-Spontaneous regardless
d) Gaswillnotobeythelawofconservationof energy
+ve. -ve +ve
to

of temparature
2. An adiabatic process is a process in which

Spontaneous only at high

a. All energy is transferred as heat
+ve +ve -ve
temparature
are

b. No energy is transferred as heat

c. The temparature of a gas decrease in a
Spontaneous only at low
-ve -ve -ve
temparature
reversible adiabatic expansion
d. B and C
sd

3. If the internal energy of an ideal gas decrease

by the same amount as the work done by the a. 1,2 only b. 1,2 and 4 only
system, the process is c. 1 and 4 only d. All of the above
aim

a. cyclic b. Isothermal 11. Identify the intensive quantity from the follow-
c. Adiabatic d. Isolated ing :
4. When the gas is ideal and the process is iso- a. Enthalpy and temparature
thermal, then b. Volume and temparature
1 1 = PV
2 2
b. E1 = E2 c
w.

a. PV . c. Enthalpy and volume

d. Temparature and refractive index
d. A and B
12. When a gas subjected to adiabatic expansion,
ww

5. Which of the following statment is correct? it gets cooled due to

a. The work done by the system on the
a. Fall in temparature
surroundings is negative
b. The work done on the system by the b. Loss in kinetic energy
surroundings is positive c. Decrease in velocity
c. The heat absorbed by the system from the d. Energy spent in doing work
surroundings is positive
d. All of the above
CHEMICAL THERMODYNAMICS & ENERGETICS
 DISHA SCIENCE ACADEMY
13. The change in internal energy of a system 23. Work done by the system in a cyclic process is
depends on equal to
a. Intial and final states of a system a. Zero b. c. d.
b. Whether the path is reversible 24. Internal energy of an ideal gas depends on
a. Pressure b. Temparature

m
c. Whether the path is irreversible
d. None of the above c. Volume d. None
25. Vibrational energy is

.co
14. The amount of heat measured for a reaction in
a bomb calorimeter is a. Partially potential and partially kinetic
b. Only potential c. Only kinetic
a. b. c. d.
d. None of the above
15. The enthalpies of elements in their standard

ot
26. All the naturally occuring processes i.e. spon-
states are taken as zero. Hence the enthalpy of
taneous processes proceed spontaneously in a
formation of a compound

sp
direction which leads to
a. Should always be negative
a. Decrease of free energy
b. Should always be positive
b. Increase of free energy

g
c. Will be equal to twice the energy of combustion
c. Decrease of entropy d. 2 & 3
d. May be positive or negative

blo
27. Select the correct limitations of IIIrd law of ther-
16. Evaporation of water is
modynamics
a. An exothermic change
a. Glassy solids at zero Kelvin has entropy
b. An endothermic change
greater than zero
c. A process where no heat change occurs

ss.
b. Solids having mixtures of isotopes do not have
d. A process accompanied by chemical reaction
entropy zero at zero Kelvin
17. Which of the following fuels will have highest
ce
calorific value (kJ/kg)? c. Crystals of do not
a. Charcoal b. Kerosene have zero entropy at zero Kelvin

3kT >N0,On
∆V, < O∆, SNO> ,0H O, etc. in water, there occurs
c. Wood d. Dung d. All the above
c

2222
RT 2a. Increase2 in free energy
18. A spontaneous reaction is impossible if q
∆
PRT
CO 28.
H
G
E
S
kT <
dissolving NaCl
su

a. Both and are negative

b. Both and are positive b.Increase in entropy
to

c. Decrease in entropy
c. is negative and is positive
d.No change in entropy
d. is positive and is negative 29. When hydrogen and oxygen burn to form water
are

19. In which of the following case, entropy decrease in an oxyhydrogen torch, the entropy change is
a. Solid changing to liquid a. -ve b. +ve c. 0 d. +ve or -ve
b. Expansion of a gas c. Crystals dissolve 30. If a refrigerator door is kept open, then we get
d. Polymerisation
sd

a. Room cooled b. Room heated

20. In which case, a spontaneous reaction is im- c. More heat is pased out
possible at any temparature d. No effect on room
aim

a. b. 31. In a reversible isothermal process, the change

c. d. In all the cases in internal energy is
a. Zero b. Positive
21. Warming ammonium chloride with sodium hy-
c. Negative d. None
droxide in a test tube is an example of
w.

32. When the value of entropy is greater, then the

a. Closed system b. Isolated system
ability for work is
c. Open system d. None of the above
a. Maximum b. Minimum
ww

22. When an ideal gas is compressed adiabatically

c. Medium d. None of these
and reversibly, the final temparature is
33. The internal energy of one mole of gas is
a. Higher than the intial temprature
b. Lower than the intial temparature
a. b. c. d.
c. The same as the intial temparature
d. Dependent on the system of compression

CHEMICAL THERMODYNAMICS & ENERGETICS

 DISHA SCIENCE ACADEMY
34. Which of the following statements is incorrect? 42. Mechanical work is specially important in sys-
a. The entropy of an isolated system increase in tems that contain
an irreversible process a. solid - liquid b. liquid - liquid
b. The entropy of an isolated system remains c. solid - solid d. gases

m
unchanged in a reversible process
43. For the reaction
c. as well as ∆S surrounding are nega- a. ∆H > ∆E b.

.co
tive quantities c. d. None of these
d. Entropy can never decrease 44. The value of free energy change at equilibrium is
35. Choose the correct relation : a. Positive b. Negative c. Zero d. Not definite

ot
a. ∆G = ∆H + ∆nRT 45. According to third law of thermodynamics,
b. which one of the following quantities for a per-

sp
fectly crystalline solid is zero at absolute zero.
a. Entropy b. Free energy
c. c. Internal energy d. Enthalpy

g
46. Which one of the following is an extensive quantity?
d. None of these

blo
a) surface tension b) Density
36. Which of the following are thermodynamically c) Heat capacity d) Specific heat
stable? 47. Which one of the following is an intensive quantity?
a. C (diamond) b. C (graphite) a) Temperature b) Volume

ss.
c. (red) d. All are equally stable c) Number of moles d) Work
37. In which one of the following sets, all the prop- 48. Which change would have a negative value?
ce
erties belong to same category? a)
a. mass, volume, Pressure

3px24G
(kJ +(=
(+H (ymole
2)
0)(g2∆ −)
0g
)∆ ()1gCl T(∆
)−mol gS−S∂)g1 →
2(Na )∆+ 2Cl
+(Geg−)) +( gCl) −1 ( g )
b. Temparature, Pressure, Volume b)
1< 1T
c
2→

2G = ∆H
max
→ S2∆S
d) Cl ( g ) +∂eT− → Cl − ( g )
c. Heat capacity, density, entropy ∆
V
C ∆
HI
HBr
IR
P
w
Na
xy
JK P
T
E
H H −<
+
gpV
kJg=
O
mol>
Cl −H
c)
→
HE
mol
kJ −+
CO
Na +∆
(
su

d. Enthalpy, internal energy, volume ∆ R

external
system
+T
38. The difference between and at con-
49. Unit of entropy is
a) JK −1mole −1
stant volume is equal to :
to

b)
a. c) JK mole −1
b. c. d.
are

d) None of these
39. If the internal energy an ideal gas decreases by 50. For a spontaneous reaction which one is true?
the same amount as work done by the system, a) b)
the process is :
sd

c) d) None of these
a. cyclic b. isothermal
c. adiabatic d. isolated 51. represents calculation of at
aim

40. Select the exothermic compund among the fol- a) b)

lowing with respect to enthalpy of formation :
c) d) None of these
a. b.
52. of a system is not equal to
c. d.
w.

a) b) c) n × Q d)
41. When a gas is allowed to expand from a region
of extremely high pressure to a region of ex- 53. sublimation of graphite and diamond
ww

tremely low pressure, there occurs a change of

respectively are x and y . What is
temparature. This phenomenon is connected
with: for the change; Graphite diamond

c) ( x − y ) kJ mol −1 4) ( y − x) kJ mol −1
a. first law of thermodynamics a) b)
b. Joule Thomson effect
c. Gibbs Helmholt’z equation
d. None of the above
CHEMICAL THERMODYNAMICS & ENERGETICS
 DISHA SCIENCE ACADEMY
54. Which one of the following quantity is indepen- 5. Given

X + ( g ) → X +2 ( g ) + e− ; ∆H = 420 kJ mol −1
dent of path?
a) molar internal energy b) volume

X +2 ( g ) → X +3 ( g ) + e− ; ∆H = 3547 kJ mol −1
c) q + W d) work

m
55. Evaporation of water is
a) an exothermic process Which ion is most likely to be present in the crys-

c) an exothermic process at 1000 C

.co
b) an endothermic process talline compound formed between X and fluorine?
a) X +3 b) c) d)
d) an endothermic process at 6. For precipitation reaction of with

ot
KEY which of the following statements is correct?
1.a 2.d 3.c 4.d 5.d a) for the reaction is zero

sp
6.c 7.c 8.c 9.d 10.d b) for the reaction is negative
11.d 12.d 13.a 14.c 15.d c) for the reaction is part-time

g
16.b 17.b 18.d 19.d 20.b d)
21.c 22.c 23.d 24.b 25.a

blo
7. Entropy decreases during
26.a 27.d 28.b 29.a 30.b a) crystallization of sucrose from solution
31.a 32.a 33.a 34.c 35.c b) vaporisation of water
36.b 37.d 38.c 39.c 40.c c) Melting of ice

ss.
41.b 42.d 43.c 44.c 45.a d) Vaporization of Camphor

at 250 C are given below :

46.c 47.a 48.d 49.a 50.b 8. The enthalpy for the following reactions
ce
51.b 52.d 53.c 54.c 55.b

1∆
27
100321.3KJ
g1.13
321.3
9.91
8.78
18.69
321.30
S+(−E ) +150
900
1 (R
300
X300
vap( g ) 460.6
R)(+g )mol; ∆−OH=( g214
LEVEL-II
); 10.06
020 0 kJ 1 −1
c
. The 2 2
ii) H22 ( g ) → 2 H ( g ); 104.18 kcal
i) +
1. The heat of combustion of solid benzoicacid and ∆
(A
+
−
NaCl
X G
H HgC)
=C )∆
→
=+
−H
kJkJ
+ 2
gcal e −→ H kJ mol
su

at constant volume is at H O kcal

iii) O2 ( g ) → 2O( g ); 118.32 kcal

heat of combustion at constant pressure is
to

a) b)
c) d) Calculate the O − H bond energy in the hydroxyl
radical.
are

2. The heats of combustion of yellow P and red P

a. - 101.19 kcal b. + 206.13 kcal
are and respectively. The
c. - 206.13 kcal d. + 101.19 kcal
heat of transition of yellow to red phosporus is 9. If 50 calorie are added to a system does work
sd

a) b) of 30 calorie on surroundings, the change in in-

c) d) ternal energy of system is
a. 20 cal b. 50 cal c. 40 cal d. 30 cal
aim

3. of a reaction
a) Depends only on the nature of the reactants 10. Latent heat of vaporisation of a liquid at 500 K
b) Depends only on the nature of the products and 1 atm. pressure is 10.0 kcal/mol. What will
c) Depends on the nature of reactants, prod- be the change in internal energy of 3 mole
w.

ucts and path used to bring about the change of liquid at same temparature
d) Depends on the nature of reactants and the a. 13.0 kcal b. -13.0 kcal
products but not on path used to bring about c. 27.0 kcal d. -27.0 kcal
ww

the change.
11. Boiling point of a liquid is 50 K at 1 atm. and
4. Which of the following statements is true about
the entropy of the universe? . What will be its b.p.
a) Increases and tends towards maximum value at 10 atm.
b) Decreases and tends to be zero a. 150 K b. 75 K
c) Different intermediate reaction c. 100 K d. 200 K
d) Decreases and Increases with a periodic rate.
CHEMICAL THERMODYNAMICS & ENERGETICS
 DISHA SCIENCE ACADEMY
12. The expression representing Gibbs-Helmholtz 18. A hypothetical reaction proceeds
equation is : through following sequence of steps :
 ∂ ( ∆G 0 ) 
0 0
(i) (ii)
a. ∆G = ∆H + T  ∂T 2 
 

m
(iii)
Then the heat of reaction is :

.co
b. a. b.

 ∂ ( ∆G / T ) 
c. d.
0
0
c.  ∂ (1/ T )  = ∆H
19. If E,R and D represent the tendency of

ot
minimum energy(E), tendency for maximum
 p
 ∂ ( ∆G 0 / T ) 
randomness (R) and overall driving force (D)

sp
respectively and arrows represent the direction

d.   = −∆H 0 and magnitude of these tendencies, choose the

∂T  p correct option applies to following reaction :

The enthalpy of dissolution of BaCl2 ( s ) and

g


blo
13.
are and per 
→E 
→E
mole respectively. The enthalpy of hydration 
→R ←
R

(a) (b)
→D →D

ss.
for, is
a. 29.4 kJ b. -29.4 kJ
c. 11.8 kJ d. 38.2 kJ

840 J per mol and its boiling point is −1730 C .

ce
14. The enthalpy of vapourisation of a substance is ←
E ←
E

8.8
225 20.6
112∂HgO 230kJ 2(2D
(av+ 116g(−B2;)=s;0)∆
21.2
,∆
2x)0H 2per
(2HsHg
v)2O(→ 0)H O1 ( g.2
) HO ( s
) D

→R ←
R

2P +0=<
(=sB)∆;→
0= q
2l
( ) vap 2 O2 ( g ) 2
0 D
Calculate its entropy of vaporisation :
c
2  = − 2 2 ( c) 2 2 (d )
2H 4a 2g
aq∆
−∆ ( S+
−−→ )
>vsub=∆ − + J2O
→ →
+BaCl ←
Cu=− ∆
a) 8.4 Joule/K/mole C A
PH
BaCl
H H C P C H xH
H K
→ G ∆Hfus ∆ +
su

CuO D x
OH s
b) 21 Joule/K/mole
c) 49 Joule/K/mole  ∂ T  T

1
20. For the two equations given below :

(i) H 2 ( g ) + O2 ( g ) → H 2 O(l ) + a1 kJ
d) 12 Joule/K/mole
to

2
15. Which has the highest entropy per mol of the

1
substance?

(ii) H 2 ( g ) + O2 ( g ) → H 2O ( g ) + a2 kJ
are

a) H 2 at
2
at 1 atm
b) at STP
c) at 100K at 1 atm The correct relation between a1 and is :
sd

d) at 0 K at 1 atm a. b.
16. The heat of atomisation of is 228 kcal c. d.
aim

per mol and that of is 355 kcal per 21. The mathematical expression for the standard
mol. The energy of bond is : enthalpy of sublimation is given by :
a. 102 kcal per mol b. 51 kcal per mol a.
0
= ∆H 0fus − ∆H vap
0
c. 26 kcal per mol d. 204 kcal per mol
w.

17. Calculate the free energy change b. ∆H sub

0
c. ∆H sub = ∆H 0fus + ∆H vap
0

− ∆ 2 H diss
for

Give ∆H = 145.6 kJ per mol

ww

0 0 0
d. ∆H sub = ∆H comb
0 0
Here, ∆H sub = ∆H sub lim ation ;

∆H 0fus = ∆H 0fusion ; ∆H vap

0 0
a. 110.8 kJ per mol b. 221.5 kJ per mol
c. 55.4 kJ per mol d. 145.6 kJ per mol = ∆H vaporization ;
0 0
∆H diss = ∆H dissociation

CHEMICAL THERMODYNAMICS & ENERGETICS

 DISHA SCIENCE ACADEMY

frozen at 00 C .
22. The enthalpy change when 1 g of water is 30. In thermodynamics, a process is called revers-
is : ible when
a. surroundings and system change into each other
a. -1.435 cal/g b. -80.0 calg
b. there is no boundary between system and
c. 80 cal/g d. -55.6 cal/g

m
surroundings

→ ≈ 88 J / K / mole
23. Mark the incorrect relationship :
c. The surroundings are always in equilibrium
∆H
a.  

.co
vapour
Tb with the system
b. ∆H = ∆E = ∆η( g ) RT
d. the system changes into the surroundings

c. specific heat X atomic mass = 6 cal/mol 0 C

spontaneously

ot
31. Bond enthalpies of and HX are in the
d. ratio 2:1:2. If enthalpy of formation of HX is -
24. One mole of a non-ideal gas undergoes a change

sp
50 , the bond enthalpy of is
of state (2.0 atm, 3.0L 95K) (4.0 atm, 5.0L,
245K) with a change in internal energy, a. b.

g
The change in enthalpy c. d.

blo
of the process in L atm is.
a. 40.0 b. 42.3 c. 44.0 KEY
d. Not defined because pressure is not constant 1.c 2.d 3.d 4.a 5.b

ss.
25. One mole of an ideal gas at 300 K is expanded 6.b 7.a 8.d 9.a 10.c
Isothermally from an intial volume of 1 litre to 11.c 12.c 13.b 14.a 15.a
10 litres. The ∆E for this process is 16.b 17.a 18.c 19.c 20.d
ce
21.c 22.b 23.d 24.c 25.b
26.a 27.b 28.a 29.d 30.c

373k
370K
375K
2A
H
26. If 900J/g of heat is exchanged at boiling point 100
30026.4
200
400 ,=2=KJmol
=(0)f2B100
0.05
30.0
)=kcal
45.0 2 )mol
1.435
−1cal
=11Tatm−/S
(,.g−−1)1/)mol
94.05 kcal) ,
31.a
1K
c
a. 163.7 cal b. zero c. 1381.1 cal d. 9 lit atm
22H 2mol
→
(CO
−
∆
X∆
H H
U
G
S
RHfO
KJmol + ∆
lCO →
H
⇌ +C
−−
kcal
LH
kJ ∆kO
− cal
K
su

of water, then what is increase in entropy? LEVEL-III

a. 43.4 J/mole b. 87.2 J/mole 1. The specific heat of a gas is found to be 0.075
to

c. 900 J/mole d. Zero calories at constant volume and its formula wt

27. Entropy change involved in the conversion of 1 is 40. The atomicity of the gas would be:
mole of liquid water at 373 K to vapour at the
are

a) One b) Two c) Three d) four

= 2.257kJ / g )
same temparature will be 2. When 12.0 g of carbon reacted with a limited
( ∆H vap
quantity of oxygen, 57.5 kcal of heat was pro-
duced. Calculated the no. of moles of CO and
sd

a. 0.119kJ b. 0.109kJ c. 0.129kJ d.0.12kJ

109 K.cal.mole-1 . When a mole of water is ∆ H (C O ) =

28. The bond energy of an O-H bond is the no. of moles produced.
[
aim

formed
a. 218 K.cal. is released
a) 0.54 mol of CO b) 0.46 mol of CO
b. 109 K.cal. is released
c) 0.64 mol of CO d) 0.74 mol of CO
c. 218 K.cal. is absorbed
w.

3. For the reaction at 298 K ,

d. 109 K.cal. is released
and . As-
29. For the process
ww

suming and to be constant, at what

∆S = 1.20 X 10 2 Jk mol −1 .
and
minimum temperature will the reaction become
At what spontanous?

a. 273K b.
temparature the above process is at equilibrium? a) 2, 000 K b) 200 K
c. d. c) 4,000 K d) 400 K

CHEMICAL THERMODYNAMICS & ENERGETICS

 DISHA SCIENCE ACADEMY
11. Select the correct alternate about entropy
4. A reaction happens to be in state of equilibrium
at 400 K and occurs spontanously below 400 a) b)
K in forward direction. The for the pro-
c) d)
cess is . The at 400 K for

m
12. Which of the following process is spontaneous?
this process would be:
a) diffusion of perfume molecules from one side
a) b) of the room to the other

.co
c) d) b) decomposition of solid CaCO3
5. The volume of a gas expands by at a c) heat flow from a cold object to a hot object
d) climbing up a mountain

ot
constant pressure of . The work done
13. ,
is equal to

∆S 0 = 22.0 J K −1 mol −1

sp
a) b) 250 J ,
c) 250 watt d) 250 newton

a) above 0 0 C

g
6. A gas expands against a constant external pres- Formation of ice is favoured at a temperature?
sure of 2.00 atm from an initial volume of 1.50 L b) below

blo
to a final volume of 3.50 L. The container is well
c) at d) above
insulated so that no heat enters or leaves the sys-
tem. Calculate the change in internal energy ( ) 14. Following reaction occcurs at :

⇌ 2 NOCl ( g ,1× 10 −2 atm)

ss.
of the gas in joules. [1 L atm = 101 J]
a) b) c) 4.00 d) 25.3 is:
7. At a certain temperature and pressure, the re-
ce
a) b)
action is endothermic but
c) d)

a) ∆G > 0 1009
30909
100
225
lim404
809
354.4
177.2
59.4
100
10
22.82
57.06
33.5
2.5
45.65
28.53
60.5
87.5
40
174.0
0.25
71.6
200
268
107.
71.6
1000
10
027
2.47 000
( 2.303
cal/K
2.303
cal/K
cal/K
(cal/K
0
(
10 0
,10−/29
)
6.01 2
10−11150
150 300
mol ( log
( log
atm)
) 8
(
) 2)2 2log (2
( ),1 10 ( atm)
)
spontaneous. Which of the following is true?

0 2 ( g reaction
) → O3 (in g )which urea
030−=
+0>
0erg 32−1kJ 1× −5−1−
−11× 1cal −2
c
15. The change of −entropy, at 298K for the

2
2 2 2
(liquid)3 3
ice 2 ( vapour)
3 22 2 2
−
+
∆
W
SH
NH
CO
A
Cl
NaU
E
H
S
NH
KCalmol
NO
G CG S+
O
C <
S
C
Nm<
>−
×
kJ
KB
m=
=
kcal
⊙
⊙
S =
kJ
J
g
K >g
CCaCO+
s∞→S
Calmol
K
mol +
××
⇌
Calmol ×
−mole
−
COAB H
kJ sO g→
moll × +
CaOcal
Cl sg + ×
cal
CO g
su

→
T →∞rO
b) and is formed from and

→ NH 2CONH 2 (aq ) + H 2O(l ) . The standard

c) and .
to

d) and
8. A gas obsorbs 100 J of heat and is entropy of NH 2CONH 2 is
are

simulataneously compressed by a constant ex-

.
ternal pressure of 1.5 atm from 8 to 2L in vol-
ume. What is in joules for the gas? a) + 354.4 b)
c) + 177.2 d)
sd

a) b) c) d)
9. The lattice energy of solid NaCl is 180 16. for conversion of oxygen to ozone
aim

and enthalpy of solution is 1 . If the

at 298 K, if K p for this
hydration energies of and ions are in

a) 163 kJ mol
the ratio 3:2, what is enthalpy of hydration of conversion is .
−1

b. 107.4 K Calmol
sodium ion?
−1
b)
w.

a.
c) d)
c. d. 17. Fo the reaction at
ww

8g of O2 gas at
∆G 0 = −27 kJ , PCO2 0.0033 atm , hence ∆G
10. is compressed to half of ,
the volume under isothermal and reversible con-
dition. Work done on the system is:
the temperature is
a) b)
a) b)
c)
c) d)
d)
CHEMICAL THERMODYNAMICS & ENERGETICS
 DISHA SCIENCE ACADEMY
KEY 6. If liquids A and B form an ideal solution
[AIEEE 2003]
1.a 2.a 3.a 4.c 5.b
6.a 7.c 8.d 9.a 10.c a) the entropy of mixing is zero
11.c 12.a 13.b 14.a 15.b b) the free energy of mixing is zero
c) the free energy as well as the entropy of

m
16.a 17.b
mixing are each zero
Previous Questions d) the enthalpy of mixing is zero

.co
1. If an endothermic reaction is non-spontaneous 7. In an irreversible process taking place at con-
at freezing point of water and becomes feasible stant T and P and in which only pressure-vol-
at its boiling point, then [AIEEE 2002] ume work is being done, the change in Gibbs

ot
a) is -ve, is +ve free energy (dG) and change in entropy (dS),
satisfy the criteria [AIEEE 2003]
b) and both are +ve

sp
c) and both are -ve a) ,
d) is +ve, is -ve b) ,

g
2. A heat engine abosrbs heat at temperature c) ,

blo
and heat at temperature . Work done by d) ,
the engine is . This data [AIEEE 2002] 8. The correct relationship between free energy
a) violates 1st law of thermodynamics change in a reaction and the corresponding equi-

ss.
b) violates 1st law of thermodynamics is if Q1 is -ve
b) ∆G 0 = RT ln K c
librium constant is [AIEEE 2003]

c) −∆G 0 = RT ln K c d) ∆G = RT ln K c
c) violates 1st law of thermodynamics of is -ve
ce a)
d) does not violate 1st law of thermodynamics

∆H = −393J 900
2−
(<
1T 125
250
9000
(S 4010)) ln(2upon
)00CO ) c+HH0 2=( g−)142 3 ( g[AIEEE
)
3. For the reactions,
3 kJ
1−kJ −1
c
9. The entropy change for a reaction does not de-
1×
2Zn
12(c2+ 1 2
,, 2 2= 2O ( g2) ∆ 3C mol
; ∆H = −412 J
g)
; C
Q
O >
+
∆
−∆
H
JdG
KdS
mol H −
=
−
−
QC
G −
C
H
O+
H
kJ
C +
= O
e →
Q−
CH>
=
<
=→
>
RT
pend g−KZnO → HKJ − CH 2003]
su

VT EP
a) use of different reactants for the same product
[AIEEE 2002]
b) the nature of intermediate reaction steps
to

c) the differences in initial or final temperatures

a) carbon can oxidise Zn
of involved substances
b) oxidation of carbon is not feasible d) the phiscal states of reactants and products
2−
are

c) oxidation of Zn is not feasible

d) Zn can oxidise carbon 10. The formation of the oxide ion O( g ) requires
4. The internal energy change when a system goes first an exothermic and then an endothermic step
from state A to B is 40 kJ/mole. If the system as shown below [AIEEE 2004]
sd

O( g ) + e− = O(2g−) ∆H 0 = 844 KJ mol −1

goes from A to B by a reversible path and re-
turns to state A by an irreversible path what
would be the net change in internal energy?
aim

[AIEEE 2003] This is because

a) b) a) O − ion will tend to resist the addition of an-
c) Zero d) 40 k J other electron
b) Oxygen has high electron affinity
w.

5. If at 298K the bond energies of , ,

c) Oxygen is more elecronegative
and bonds are respectively
d) ion has comparatively larger size than
414, 347, 615 and 435 kJ , the value of
ww

oxygen atom

to 1 ×10 −2 m 3 at 300 K against a constant pres-

enthalpy change for the reaction 11. An ideal gas expands in volume from

sure of 1× 105 Nm −2 . The work done is

a) −250 kJ
at 298 K will be [AIEEE 2003]

b) −900 kJ c)
b) [AIEEE 2004]

c) d) a) 270 kJ d)

CHEMICAL THERMODYNAMICS & ENERGETICS

 DISHA SCIENCE ACADEMY
12. The enthalpies of combustion of carbon and 17. for the formation of carbon mon-
carbon monoxide are and oxide (CO) from its elements at 298 K is

a) 1238.78 J −1 mol −1
respectively. The enthalpy of ( ) [AIEEE 2006]
formation of carbon monoxide per mole is

a) −676.5 kJ

m
[AIEEE 2004]

c) 2477.57 J −1 mol −1
b) b)

.co
c) d)
13. For a spontaneous reaction the , equilib- d)
rium constant (K) and will be respecitvely
PREVIOUS QUESTIONS-KEY

ot
[AIEEE 2005]
a) , b) , , 1.b 2.a 3.d 4.c 5.c 6.d

sp
c) , , d) , > 1, 7.a 8.c 9.b 10.a 11.c 12.b
14. Consider the reaction: 13.a 14.c 15.d 16.d 17.d
carried out at constant temperature and pres-

g
sure. If ∆H and are the enthalpy and in- LEVEL-2-HINTS & SOLUTIONS

blo
ternal energy changes for the reaction, which of 8.
the following expression is true [AIEEE 2005]
9. ∆U = Q + W
a) b)
c) d) 10.

ss.
15. An ideal gas is allowed to expand both revers-
ibly and irreversibly in an isolated system, If 11.
ce
(log =f=P)2.303 ( )
is the initial temperature and is the final tem-

110.5
< >
228 ve
ve,
393.5
110.5
(1238.78
676.5 01 1 0 −)1P
( PV −11V −(1∆
V−1 = 0)
3 f2477.57
283
74.8 3T
>8.314 3 2vap 3g1)1 21 )1 
log
−1−∆ −1H
16. bond energy =
c
perature, which of the following statements is
2irrev
(rev
 3f P revT 2.303
22=2+ (ilH)E2J1mol 2H
∆(mol 22)2O
SCell
correct? T −
+
∆−
∆
P
H∆
NT
E
R H H
E
UG −H = =
H
O<
>
= −
T∆∆
kJ ∆
kJ
T ∆ ∆
kJ
E
H
UU
⇌+
∆
S++
→
+
>JHP H NH − PV
ikJ
[AIEEE 2006] mol
JK T mol mol
=
su

W iT
f24. =  f  − 
T
nRT
irrevT V1 T
i
1  1 2 
 R
a) for reversible process but
Q
for irreversible process 26. ∆S =
to

T
b)
are

27.
c) for both reversible and irreversible process
LEVEL-3-HINTS & SOLUTIONS

Cv = 0.075 × at w.t
The standard enthalpy of formation (∆ f H 0 )
d) Cp
sd

1. =γ

at 298 K for methane. CH 4 ( g ) is

16. Cv
aim

3.
. The additional information
4.
required to determine the average energy for
C − H bond formation would be 5. W = P ∆V
w.

[AIEEE 2006]
a) latent heat of vapourization of methane 6.
b) the first four ionization energies of carbon 8.
ww

and eectron gain enthalpy of hydrogen 10. Heat of solution = L E + H. E

c) the dissociation energy of hydrogen molucule,
d) the dissociation energy of and enthalpy 11.

∆G = ∆G 0 + 2.303 RT log K p
of sublimation of carbon.
19.

CHEMICAL THERMODYNAMICS & ENERGETICS