GPCC, Nk

204
Volume-I
6. THERMODYNAMICS

SYNOPSIS :

the remaining
System, Surroundings and Boundary : observation is called the system and
Aspecified part of the universe which is under called the surroundings.
portion of the universe which is not a part of the systemis imaginary boundaries. The boundary also
The system and the surroundings are separated by real or interact across the
boundary.
surroundings can
defines the limits of the system. The system and the
Types ofsystems : boundary is sealed
type of system has no interaction with its surroundings. The contained in
usystem : This with surrounding. Asubstance
and insulated. Neither matter nor energy can be exchanged
an ideal thermos flask is an example of an isolated system. but not
of system can exchange energy in the form of heat, work or radiations
insulated.
*oseu system: This type surroundingsis sealed but not
matter with its surroundings. The boundary between system and
For example, liquid in contact with vapour ina sealed tube and pressure cooker.
matter as well as energy with its surroundngs. 1he
m) open system : This type of system can exchange
water in an open beaker is an example of open
boundary is neither sealed nor insulated. Sodium reacting with
system. throughout.
) Homnogeneous system :A system is said to be
homogeneous when it is completely uniform
a pure single solid, liquid or gas, mixture
A homogeneous system is made of one phase only. Examples:
of gases and a true solution.
uniformthroughout, i.e., it
) Heterogeneoussystem:A system is said to be heterogeneous when it is not
two or more immiscible liquids,
consist of two or more phases. Examples : ice in contact with water,
insoluble solid in contact with a liquid, a liquid in contact with vapour, etc.
number of particles (may
vi) Macroscopic system : A macroscopic system is one in which there are a large
be molecules, atoms, ions etc. )

Macroscopic properties of the system :

Thermodynamics deals with matter in terms of bulk (large number of chemical species) behaviou.
The properties of the system which arise from the bulk behaviour of matter are called macroscopic
properties.
The common examples of macroscopic properties are pressure, volume, temperature, surface tension,
viscosity, density, refractive index, etc.
types
The macroscopic properties can be subdivided into two
) Intensive properties :The properties which do not depend upon the quantity of matter present in the
SVstem or size of the system are called intensive properties. lts examples are pressure, temperature,
density, specific heat, surface tension, refractive index, viscosity, melting point, boiling point,
volume per mole, concentratjon etc.
Extensive properties :The properties whose magnitude depends upon the quantity of matter present
in the svstem are called extensive properties. ltS examples arejtotal mass, volume, intermal energy,
nature.
enthalpy,entropý,etc. These properties are additive in
Anyextensive property if expressed as per mole or per gram becomes an intensive property.
 Volume-1 205
State ofa system and state GPCC, Nkl
variables :
Macroscopic properties which determine the state of
functions or thermodynamic a system are referred to as state variables or state
parameters.
1ne change in the state properties depends only unon the initial and final states of ne systo
independent of the manner in which the change has
been brought
properties do not depend upon a path about.
In other words, the state
followed.
Thermodynamic equilibriumn :
h System is said to have attained a state of thermodynamic
equilibrium when it shows no rurner
tendency change its property with time".
to
Ine criterion for thermodynamic equilibrium requires that the following three types of
simultaneously in asystem, equilibrium exist
9 Chemical Equilibrium: A system in which the composition of the system
remains fixed and deinte.
u) Mechanical Equilibrium : No chemical work is done between different parts of the
system or
Detween the system and surrounding. It can be achieved by keeping pressure constant.
4 nernal Equilibrium : Temperature remains constant i.e. no flow of heat between system and
surrounding.
Thermodynamic process:
When the thermodynamic system changes from one state to another, the operation is called a process.
The various types of the processes are
) lsothermalprocess: In this process operation is done at constant temperature. dT =0 thus AE-0.
i) Adiabatic process: In this process there is no exchange of heat takes place between the system and
surroundings. The system is thermally isolated, i.e., dq =0 and its boundaries are insulated.
itt) Isobaricprocess: In this process the pressure remains constant throughout the change i.e., dP =0.
iv) Isochoricprocess: In this process volume remains constant throughout the change, i.e.,dV = 0.
v) Cyclic process: When a system undergoes a number of different processes and finally return to its
initial state, it is termed cyclic process. For a cyclic process dE=0 and dH=0.
vi) Reversible process: A process which occurs. infinitesimally slowly, i.e. opposing force is
infinitesimally smaller than driving force and when infinitesimal increase in the opposing force can
reverse the process, it is said to be reversible process.
vi) Irreversible process: When the process occurs from initial to final state in single step in finite time
and cannot be reversed, it is termed an irreversible process. Amount of entropy increases in
irreversible proces.
Ireversible processes are spontaneous in nature. All natural processes are ireversible in nature

Internal energy, Heat and ork :

1) Internal energy (E) :
<«Fvery system having some quantity of matter 1s assOCiated with adefinite amount of energy. This
energy isknown as internalenergy.
E=Erranslational t Erotational t Evibrational Ebonding + Eelectronie t.....

Characteristics of internalenergy :
anextensive property.
i) Internal energy of a system is
property.
ü) Internal energy is a state the final state is reached
iii) The change in the intenal ener8y does not aepend on the path by which
 Volume -| 206
GPCC, Nkl
iv) There is no change in intermal cnergy in a
cyclic
process.
" e internal energy of aF ideal gas is a function of temperature only. temperature,
ciergy of a system depends upon the quantity of substance, its chemical nature,
pressure and volume.
vii)The unit of E is ergs inCGS or joules in SI
1Joule = 10'ergs.
of
eg mternal energy (AE): t is neither nossible nor necessary to calculate the absolute value
intenalenergy of asystem then, AE =E,- Em: AE is positive if E;- Ej, and negative if E Ein
2) Heat (q) and Work (w):
The energy of a system may increase or decrease in several ways but two common ways are ea and
work.
Heat is a form of energy. It flows from one system to another because of the difference in termperdure
between them. Heat flows from higher temperature to lower temperature. Therefore, it is regarded as
energy on the move.
"o S Sald to be pertormed if the point of application of force is displaced in the direction of the force.
ltis equal tothe force multiplied by the displacement (distance through which the force acts).
There are three main types of work which we generally come across. These are gravitational work,
electrical work and mechanical work.
Mechanical work= Force x displacement =F.d
Electrical work =potential differencex charge =V.q
Gravitational work=mgh
Units of heat and work: The heat changes are measured in calories (cal), Kilo calories (kcal), joules (J)
or kilo joules (kJ). These are related as, 1cal =4.184 J; Ikcal = 4.184kJ
The S.I. unit of heat is joule (J) or kilojoule. The Joule () is equal to Newton - metre (1 J=1Nm).
Work is measured in terms of ergs or joules. The S.I. unit of work is Joule.
1Joule = 10 ergs =0.2390 cal.
lcal> 1joule >1 erg
Sign conventions for heat and work
Heat absorbed by the system =qpositive
Heat evolved by the system =qnegative
Work done on the system =w positive
Work done by the system =W negative

First law of thermodynamics :

Helmholtz and Robert Mayer proposed first law of thermodynamics. This law is also known as law of
conservation of energy. It states that,
"Energy can neither be created nor destroyed although it can be converted from one form into another.
E- E = AE =q+ w
Le. (Change in internal energy) = (Heat added to the system) +(Work done on the systenm)
Ifa system does work (w) on the surroundings, its internal energy decreases. In this case.
AE = q+ (-w) =q- W
ie (Change in internalenergy)=(Heat added to the system) - (work done by the system)
The relationship between internal energy, work and heat is a mathematical statement of frst law of
thermodynamics.
Volume -I 207 GPCC, Nkl
Enthalpy and Enthapy change :
Heatcontent of asystem at constant pressure is called enthalpy denoted by H.
From first law of
thermodynamics,q=
Heat change at constant pressure can be E+ PV
(i)
Aq =AE+ PAV
given as
......(i1)
Atconstant pressure heat can be
replaced at enthalpy.
AH =AE + PAV .........(i11)
.AH=Heat change or heat of reaction (in chemical process) at constant pressure
AE - Heat change or heat of reaction at
constant volume.
In case of solids and liquids participating in a
reaction,
AH = AE (PAV 0)
Ditterence between AH and AE is significant when gases are involved in chemical reaction.
AH =AE + PAV
AH = AE + AnRT
PAV = AnRT
Here, An = np-nR

Specific and Molar heat capacity :

Specific heat (or specific heat capacity) of a substance is the quantity of heat (in calories, joules,
1°C. It can
kilocarlories, or kilo joules) required to raise the temperature of lg of that substance throngh
be measured at constant pressure (C) and at constant volume (C).
temperature of 1 mole of
Molar heat capacity of a substance is the quantity of heat required to raise the
the substance by 1°C.
Mand C,=Chx M.
.. Molar heat capacity = Specific heat capacity x Molecular weight, i.e., Cy =Cyxunder
heated constant pressure
Since gases on heating show considerable tendency towards expansion if
temperature by 1°C relative to that
conditions, an additional energy has to be supplied for raising its
required under constant volume conditions, i.e.,
Co> Cy or Cp =Cy t work done in expansion, PAV(=R)
where, C= molar heat capacity at constant pressure
Cy= molar heat capacity at constant volume.
Some useful relations of Ch and Cy
Co-Cy =R=2 calories =8.314 J
2-y (Ratio of molar capacities)
C,
triaomic molecules can be given as below.
The value of 'y' for monoatomic, diatomic and

Atomicity CP Cy

5 3
Monoatomic PR R 1.66
2

Diatomic 1.40
2 2
4R 3R 1.33
Triatomic
 Reversible/
Irreversíble
Irreversible 208
nCy4T nCpAT nC,AT W=0
isochoric
=0 +0 #0 =0 AU

= =
P

Reversible/ w=-Pext^V
isobaric
=0 #0=0 0 nCyATnCpAT AH =
nCpAT

relations
ofReversible
Irreversible nRT,
nRT,
nCy^T
nRT,P =nC.V,-Py)thethese

by
T,P,
P nCy4TnCpAT calculate Adiabatic
process
=0 #0*00
WIre nRT,P,
=-PextAV datarelations
only.
nR

Adiabatic
lelelel -Pext.AV
nCy4T
=
P, =-PeÁV unknown
use

=-Pet Where Don't

PV=
TVY
= Töp=
constant
constant
constant
-Py,)
P,V, -PV,)
(P,V, find
: Reversible
processes nCyATnCpAT TVY=TYp
constant
constant
=0 0 +0 #0 nCyAT
WRey nR PV=
constant to data
unknown
0
Where
use relations
thermodynamic nCy y-1
1
=
=nRT (Real
Gas)
+0
Irreversible (Real
Gas) =-Pext(V2-V)
(ideal)=0
=0 (ideal) -PexdV
=
various P,VP,V, =
-Wire -qIrev
=
=) =) 0 0 0 +0

+0
in
andw
Isothermal =
PV
Q
AH, nRT
log2
nRT
=-2.303
AU, = Gas) (Real
+0
(Real 0Gas)
AP,AV, Reversible P,V; =0
(ideal)(ideal)
=0
=0 =0 =
-WRev -qRev
Wmax
#0 0 0
PV = =
An,,AT,
=
PV
of
Calculation
Relation
P.T.V AU AH
meter
Para AT AP AV
W
 Volume-l 209
Second law of GPCC, Nk
All the thermodynamics
limitations of the
:
first
law of thermodynamics can be removed by the second law of
nemodynamics. This law is generalisation of cetain exneriences about heat engines and
reir1gerators.
nas ocen stated in anumber of wavs. but all the
statements are logicallyequivalent to one anonet.
Entropy and Entropy change :
1) Definition :
the molecules Entropy
is a
thermodynamic state quantity
of the system.
which is a measure of randomness or disorder of
Entropy is represented by the symbol "S". It is difficult to define the actual entropy of asystem. It is
more convenient to define the change of entropy
during a change of state.
Lne entropy change of a system may be defined as the integral of all the terms involving heat
(99 diided by the absolute temperature (T) during each infinitesimally small change of the exchanged
carried out process
reversibly at constant temperature.
AS = Sfnal -Sinibal = Irey
T
If heat is absorbed, then AS=+ye and if heat is evolved.,
then AS = -ve.
) Onits of entropy : Since entropy change is expressed by a heat term divided by
temperature, 1t 1s
expressed in terms of calorie per degree, i.e., cal deg.In SI units, the entropy is expressed in terms of
Joule per Kelvin, i.e., JK.
3) Characteristics of entropy : The important characteristics of entropy are summed up below
Ehtropy is an extensive property. Its value depends upon the amount of the substance present in the
system.
Entropy of asystem is astate function. It depends upon the state variables (T, P, V,n).
The change in entropy in going from one state to another is independent of the path.
The change in entropy for a cyclic process is always zero.
The total entropy change of an isolated system is equal to the entropy change of system and entropy
change of the surroundings. The sum is called entropy change of universe.
AS,universe =ASsys t ASSur
i) In areversible process, AS,universe Oand, therefore ASsy -ASSún
ii) In an ireversible process, AS,universe > 0. This means that there is increase in entropy of universe is a
spontaneous change.
Entropy is a measure of unavailable energy for useful work.
Unavailable energy = Entropy x Temperature
4) Entropy change in isothermalprocess :
Isothermal
AS
Reversible expansion Irreversible expansion
ASsys oon 2.303nR
2.303nR log 2.303nR log (or) 2.303nR log
-2.303nR logo(or)-2.303nR log P -Pea. (V, -V,)
ASsur T

tve,
0
ASTotal (ASsys. > ASsur.)
(for spontaneous process)
Volume-1
5) Entropy
Change During 210 GPCC, Nk
Phase
Transformation :
Process Equation ASTøtal AGys
A,Hy ASy AS,urr. at eg at eq
Allotropic -Ve or
change i.c. Aj A, +ve = A,Hy, A,Hys =0 -0
transition T,
Physical AHran
change
reactions S
Tsub. +ve
= Algub Agub Tsub
=0 -0
a) Sublimation Tsub
b) Fusion Tm.p +ye
= AHfusion
AHfusion AHfusion =0
Tmp
c) Vaporization +ve
L g
=AHyap.
AHyap. =0 -0

Entropy change in mixing of ideal gases :

Let nË moles of gas A and Dp moles of gas B are
mixed, then total entropy change can be calculated as
AS(for n moles) =-2.303 R[n, logX +n, log X] =-2.303 Zn, log X;
AS(for one mole) =-2.303 R|X, logX, +X log
X]=-2.303 EX, log X
XA and X¡ are mole fractions of gases A and B.

Free energy and Free energy change :

Gibb's free energy (G)is a state function and is a
measure of maximum work done or useful work done
from a reversible reaction at constant temperature and
pressure.
1) Characteristics of free energy:
The free energy ofa system is the enthalpy of the system
minus the product of absolute temperature and
entropy i.e., G= H- TS
Like other state functions E, H and S, it is also
expressed as AG. Also AG= AH-TASSwlem where AS is
entropy change for system only. This is Gibb's Helmholtz equation.
At equilibrium AG=0
i) For a spontaneous process decrease in iree energy is noticed i.e., AG =-ye
ii) AGOreaction AGfproducts -EAG;reactants AGof elements in naturally occurring state is
zero. AG of O:(g),
Fe(s), Brz()=0.
ii) Thestandard free energy change,
AG° =-2.303RT log1o K, where K is equilibrium constant.
The if K>l. then AG = -ve thus reactions with
equilibrium constant K> l are themodynamically
spontaneous.
TE K< 1. then AG° = tve and thus reacdons Whn
equillbrium constant K<lare thernodvnamically
spontaneous in reverse direction.
 Volume-1
2) 211 GPCCc, Nki
Criteria for
spontaneity of reaction: For a spontaneous change AG -ve and therefore use of
AG = AH - TAS, provides the following conditions for a change to be spontancous.
AH signAS sign AG sign Reaction condítion
1) -ve tve -Ve Spontaneous at any temperature
+ve -Ve +ve Non-spontaneous at any temperature
2) tve +ve -Ve Spontaneous only at high temperature
-Ve
-ve +ve Non-spontaneous only at high temperature
3) -ve -Ve -Ve Spontaneous only at low temperature
+ve tve Non-spontaneous only at low temperature
+ve

Thermochemistry:
Ihermochemistry is a branch of physical chemistry which is concerned with energy changes
accompanying chemical transformation.It is also termed as chemical energetics. It is based on the first
law of thermodynamics."

Exothermic and Endothermic reactions :

Exothermic reactions : The chemical reactions which proceed with the evolution of heat energy are
called exXothermic reactions. The heat energy produced during the reactions is indicated by writing tq or
more precisely by giving the actual numerical value on the products side. In general exothermic
reactions may be represented as, A+B C+D+q (heat energy)
In the exothermic reactions the enthalpy of the products will be less than the enthalpy of the reactants, so
that the enthalpy change is negative as shown below AH = H-H,; H,<H,; AH= -ve
Examples:
C(s) + O(g)> COg) + 393.5 kJ (at constant temperature and pressure)
or C(s) + Oz(g) ’ COz(g); AH =-393.5 kJ

H(g) +O:(g)
2
-’ H,0(1) ; AH =-285.8 kJ
Endothermic reactions : The chemical reactions which proceed with the absorption of heat energy are
caled endothermic reactions. Since the heat is added to the reactants in these reactions, the heat absorbed
is indicated byeither putting () or by writing the actual numerical value of heat on the reactant side
A+B’C+D-q (heat energy)
The heat absorbed at constant temperature and constant pressure measures enthalpy change. Because of
the absorption of heat, the enthalpy of protucts will be more than the enthalpy of the reactants,
Consequently, AH will be positive (+ve) for the endothermic reactions.
AH= H, - H,; H, > H; AH = tve
Example :
N2lg) + Oz(g)’ 2NO(g); AH= +180.5kJ
C(s) + 2S(s) ’ CS2(1), AH=+92.0 kJ
Preparation of ozone by passing silent electric discharged through oxygen.
Evaporation of water.
For exothermic reaction :AH or AE= -ve
+ve
For endothermic reaction : AH or AE =
 Volume 212 GPCC, NkI
Heat ofreaction or enthalpy of
reaction :
eacton is defined as the ainount of beot eualved or ahsorhed when quantities of the substances
indicated by the chemical equation have completely reacted. The heat of reaction (or enthalpy of
reaction) is actually the difference between the enthalpies ofof the products and the reactants when the
quantities of the reactants indicated by the chemical equation have completely reacted. Mathematically,
Enthalpy of reaction (heat of reaction) = AH = 2Hp - ZHR
Types ofheat of reaction:
9 Heat of formation : It is the quantity of beat evalved or ahsorbed Ge. the change in enthalpy) wnen one
mole of the substance is formed from its constituent elements under given conditions of temperature and
pressure. It is represented by AH: When the temperature and pressure are 25°Cand I atmosperne
pressure. The heat of formation under these conditions is called standard heat of formation. It 1S usually
represented by AH°.
The standard heat of formation of l mole of NH(g) and 1mole of HCIg).

N(g) + H(g)
2
’ NH;(g) ; AH= -1lkcal
1
Ha(g) + Cl,(g)
2
’ HCI; AHP=22 kcal
It may be calculated by
AH° = (EAH (products) - £AHO(Reactants)
Standard heat of formation of elements in naturally occurring state is zero. AH; 0,(g), AI(S), Brz()=0
Note AHf of C(gr) and S(Rh) are =0
i) Heat of combustion : It is the amount of heat evolved (i.e. change in enthalpy) when one mole of the
substance is completely burnt in air or oxygen. For example
CH4(g) + 202(g) ’ CO(g) + 2H,0(1) ; AH = -192 kcal
C;Hs(g)+3.5 Oz(g) 2C02(g) + 3H,O1); AH =372.8 kcal
It may be calculated by

AH° =SAH(pradisa) - EAB(Resctants)

The enthalpy or heat of combustion have anumber of applications. Some of these are described below,
Calorific value of foods and fuels: Energy is needed for the working of all machines. Even human body
is no exception. Coal, petroleum, natural gas etc. serve as the principal sources of energy for man-made
machines, the food which we eat serves as a source of energy to our body.
The energy released by the combustion of foods or fuels is usually compared in terms of their
combustion energies per gram. It is known aS calorific value. The amount of heat produced in calorieg or
oxidised
Joules when one gram of a substance (food or fuel) is completely burnt or
released.
When methane burns, 890.3 kJmol" of energy is
CH, (8)+20,(g)’Co,(g) +2H,0(); AHcH, =-890.3kJ
Imole(16g)
890.3
= .= -55.6kJ/g
So, the calorific value of methane 16

Eothalbies of formation: Enthalpies of formation of various compounds, which are notofdirectly obtained,
Heese la.
can he calculated from the data of enthalpies of combustions easily by the application
Heat of reaction = ZHeat of combustion of reactants - 2 Heat of combustion of nrodueto
Volume -1 GPCC,Nki
Heat of neutralisation : It is the amount of heat213
evolved I(i.e.,changein enthalpy) when one equivalent
reactions
of an acid is neutralised by one dilute solution, e.g., Neutralisation
equivalenttof a base in fairly
are always exothermic reaction and the value of AH is (-ve).
HCl(aq.) + NaOH(aq.)’ NaCl(aq.) +H;0
AH =-13.7 kcal
The heat of neutralisation of a strong acid constant (13.7kcal or 57kJ
against astrong base is always
qv ). tis because in dilute solutions all strong acids and bases ionise completely and thus the neat ol
neutralisation in such cases is actually the heat of formation of water from H and OH 1ons, 1e
H"+ OH’H,0:; AH =-13.7 kcal
respectively, Since a
es ueutalisation of aweak acid or a weak base against astrong base or acid
less than 13.7 kcal mol
Patol ne evolved heat is used up in ionising the weak acid or base. it is always
(57kJ g equiv ). For example,
HCN (aq.) +NaOH (aq.) ’ NaCN(aq.) +H,0
AH =-2.9 kcal

HCN(ag.)H+ CN;AH= 10.8 kcal/mol

T0.8 kcal of heat is absorbed for jonization ofHCN. It is heat of dissociation or ionization
in enthalpy)when one mole
i) Heat of solution : It: tl, :mount of heat evolved or absorbed (i.e., change
of the solute is lls.. "pletely in excess of the solvent (usually water).
For example,
NH,CI(S) + H,0(1) ’ NH,C(ag.) ; AH =+3.90 kcal/mol
BaClb(s) + H,0(1) ’ BaClz(ag.); AH = -2.70 kcal/mol
enthalpy) when Imole of
v) Heat of hydration : It is the amount of heat evolved or absorbed (i.e change in
moles of water to form a
an anhydrous or a partially hydrated salt combines with the required number of
specific hydrate.
For example,
CuSO(s) + SH,0)’ CuSO4. SH,0(s); AH =-18.69 kcal/mol
surroundings
vi) Heat of vapourisation : When a liquid is allowed to evaporate, it absorbs heat from the
increase in
and evaporation is accompanied by increase in enthalpy. For example: 10.5 kcals is the
enthalpy when one mole of water is allowed to evaporate at 25°C. When the vapours are allowed to
condense to liquid state, the heat is evolved.and condensation of vapour is accompanied by decrease in
enthalpy.
The evaporation and condensation can be represented as,
H,0() ’ H,0(g); AH =+10.5 kcal (+43.93 kJ)
H,O(g)’ H,01); AH=-10.5 kcal (-43.93 kJ)
Thus the change in enthalpy when a liquid changes into vapour state or when vapour changes into liquid
state is called heat of vapourisation.
vi) Heat of fusion:When a solid is allowed to melt, it changes into liquid state with the absorption of heat
Gincrease in enthalpy) The change in enthalpy of such type of transformations is called enthalpy of
fusion. For example,
H,O(ice)’ H,0(liquid) ; AH=+1.44 kcal/mol (+6.02 kJ)
vii)Heat of precipitation : It is defined as the amount of heat liberated in the precipitation of one mole of a
sparingly soluble substance when solutions of suitable electrolytes are mixed, for example
Ba + SO, (ag) ’ BaSO4(s) : AH=4.66 kcal/mol
 GPCC, NkI
Volume-1 214 into gaseous
ix) Heat of sublimation : Sublimation is a process in which a solid on heating changes directly
state below its melting point. of I mole of solid
Heat of sublimation of a substance is the amount of heat absorbed in the conversion
directly into vapour phase.
I,(s) ’ lh(g): AH = +62.39 kJ/mol
Most solids that sublime are molecular in nature e.g. jodine and naphthalene ete.
AHsub AHAusion t AHyaporisation
evolved or absorbed in a chemical reaction
EXperimental determination of the heat of reaction The heat principle of
in an apnaratus called calorimeter. The
S casured by carrying out the reaction 1)
measurement is that heat given out is equal to heat taken. i.e.. O = (W+ m)x sx(12-
equivalent of the calorimeter and m 1s the
where Qis the heat of the reaction (given out), W is the water
temperature and IË he mual
mass of liquid in the calorimeter andsits specific heat. T is the final
tyPes are,
temperature of the system. Different types of calorimeters are used but two of the common
(i) Water calorimeter and (i) Bomb calorimeter
organic substances. Since
Bomb calorimeter : This is commonly used to find the heat of combustion of
is AE
the reaction in a bomb calorimeter proceeds at constant volume. the heat of combustion measured
AE =
(W +m)(t, -t,)xs -xM kcal= GMWt -xC,x AT
W wt
Where M is the molecular mass of the substance, w is the weight of substance taken, W is the water
equivalent of calorimeter, mis the mass of liquid in the calorimeter and sis the specific heat of liquid.
AH can be calculated from the relation, AH = AE + AngRT

Laws ofthermo chemistry :

1) Lavoisier and Laplace law : According to this law enthalpy of decomposition of a compound is
numerically equal to the enthalpy of formation of that compound with opposite sign, For example,
C(s) +O’ CO;(g); AH=94.3 kcal/mol
CO;(g)’ C(s) +O:(g); AH=+94.3 kcal/mol
2) Hess's law (the law of constant heat summation): This law was presented by Hess in 1840. According
to this law "If a chemical reaction can be made to take place in a number of ways in one or in several
steps,the total enthalpy change (total heat change) is always the same, i.e. the total enthalpy change is
independent of intermediate steps involved in the change." The enthalpy change of a chemical reaction
depends on the initial and final stages only. Let a substance Abe changed in three steps to D with
enthalnychange from Ato B, AHË calorie, from B to C, AH, calorie and from C to D. AHa calorie Total
onthalny change from A to D will be equal to the sum of enthalpies involved in various steps, Total
enthalpy change AHsteps,= AH, + AH, + AH.
Applications of Hess's law :
a For fhe determination of enthalpies of formation of those compounds which
cannot be prepared
directly from the elements easily using enthalpies of combustion of compounds
i) For the determination of enthalpies of extremely slow reactions.
ii) Eor the determination of enthalpies of transtormation of one allotropic form into another
iv) For the determination of bond energies.
AHion=2 Bond energies of reactants - 2Bond energies of products
) For the determination of resonance energy.
vi) For the determination of lattice energy.
Volume -l 215 GPCC, NkI
Bond energy of bond enthalpies :
When a bond is fomed between atons. eneroy is raleased Obviously same
amount OL Gb
Tequred to break the bond. The enerov mauirod tn bveak the bond is termed bond dissociation energ.
The more precise definition is,
ne amount of energy required to break one mole of bond of aparticular type between he atoma
gaseous Stare, 1.e., to separate the atoms in the gaseous state under 1atmospheriC pressu a
specified temperature is called bond dissociation energy."
For example,
H- H(g)’2H(g) ; AH =+433 kJ mol
Cl- Cl(g)’ 2Cl(g); AH =+242.5 kJ mol
H-Cl(g)’ H(g) + Clg);AH=+431 kJ mol
lhe bond dissociation energy of a diatomic molecule is also called bond energy. However, the bond
issoc1ation energy depends upon the nature of bond and also the molecule in which the bond is present.
When a molecule of a compound contains more than one bond of the same kind, the average value or tne
dissociation energies of a given bond is taken. This average bond dissociation energy required to break
each bond in a compound is called bond energy.
Bond energy is also called, the heat of formation of the bond from gaseous atoms constituting the bond
with reverse sign.
H(g) + Cl(g) ’ H-CI(g); AH =431 kJ mol
Bond energy of H- Cl ={enthalpy of formation) =-431)= +431 kJ mol"
Consider the dissociation of water molecule which consists of two O -H bonds. The dissociation occurs
in two stages.
H,0(g) ’ H(g) + OH(g);AH=497.89 kJ molr
OH(g) ’ H(g) + 0(g); AH=428.5 kJ mol!
The average of these two bond dissociation energies gives the value of bond energy of 0-H.
497.8+428.5
Bond energy of O-H bond = 463.15 kJ mol'
2
Similarly, the bond energy of N- Hbond in NH, is equal to one - third of the energy of dissociation of
NH, and those ofC- Hbond in CHË is equal to one - fourth of the energy of dissociation of CHA.
1664
Bond energy of C-H= 4 -= 416 kJ mol'

[CH4(g) ’ C(g) + 4H(g); AH= 1664 kJ mol'

Theromo chemistry conculsions :

In reaction :Reactants ’ Products

1) A,H= E(AH)products2(AH)rescants
2) A,H = Z(AHcomb )resctants -E(AH,combproducts
3) A,H = 2(BE),eactant's 2(BE)products
Volume-1
QUESTIONS :
216 GPCC, Nkl

6.1 Thermodynamic Terms and Processes

1. If 'x and y' are is an intensive
1S an
extensive properties then x/y 9. Which of the following
) extensive property property?
1)Volume 2) Pressure
2)intensive property 4) Enthalpy
3)not defined 3) Entrop y
function as
4)both (1) and (2) 10. Which of the following is a state
2. The state function well as an extensive property!
among the following is a) Temperature b) Internal energy
1) dq 2) dw
3) dE c) Entropy d) Heat capacity
4) none of these 2) b, c and d
3. Changes in a system fom an initial state to the 1)a, b, c and d
final state were made by a 3) a, c and d 4) a and b
different manner
that AH remains same but q 11. Which are extensive properties
changes
1) AH is a path function but q isbecause. 2) V and T
a state 1)V and E
function 3) Vand Cp 4)P and T
2) AH is a state function and q is a 12. Which of the following is incorrect w.r.t first
path
function
law of thermodynamics?
3) Both AH and q are state functions
1) AE = 4, isochoric process
4) Both AH and q are path functions
4. In thermodynamics, a process is 2) W= AE, adiabatic process
reversible when
called 3) q=-W, isothermal process
1)The surroundings and the system change 4)q = W, cyclic process
into each other 13. Which of the following is correct statement(s)
2) There is no boundary between the system ) Pencil cell is a closed system
and the surrounding II) Human body is an open system
3) The surroundings are always in equilibrium II)EMF of a cell is an intensive property
with the system IV)Internal energy, Gibbs free energy, entropy
4) The system changes into the surroundings are extensive properties
spontaneously. V) The order of work done during
5. AUis equal to expansion
in various process is in the order of
1) Isochoric work 2) Isobaric work Wisobaric > Wisothermal > Wadiabatic >Wisochoric
3) Adiabatic work 4) Isothermal work 1))I, II, V
6 In an isochoric process, the increase in internal 2) I, II, IV
3) I, II, II, IV,V 4) I, II, III, IV
energy is equal to
1) the sum of heat absorbed and work done
14. In the graph the B and C
respectively
represent
2) heat absorbed
3)the work done
4) heat evolved B
P
7. Out of boiling point (1), entropy (), pH (II)
and density (IV), intensive properties are
1)I, II 2) I, II, III
3)I, III, IV 4) Allof these 1)Isobaric and Isochoric
8. In the thermodynamics, which one of the
2) Isochoric and Isobaric
following is not an intensive property?
3)Isothermal and
1) pressure 2) density adiabatic
4) Adiabatic and
3) volume 4) temperature isothermal
 Volume -l GPCC, NkI
45. Which is an 217
ireversible process?
A) Mixing of two gases by The correct answer

B) Evaporation of water atdiffusion 1)A, B 2) B, C

373K and latm 3)A, B, C 4) A,C, D
pressure
C) Dissolution of NaCl in
water
D) Burning of Coal

Answer Key &Solutions (6.1)

Answer Key
1
234 5 678 910 11 12 13 14 15
2 3 2 3 3 4 3 4
3 3 2 1

Solutions
1. The ratio of extensive is an
intensive property. 7. Boiling point, pH & density are intensive
2. dq and dw are path functions dE is the state properties. Entropy is an extensive property.
function. 8. Volume depends upon the quantity (extensive
3. As AH remains same by different paths, it is a property). Others are intensive properties.
state function. As q changes by different 9. Internsive property does not depend on
paths, i.e., it is a path function. quantity of substance
4. Definition of reversible process 10. Temperature is state function but intensive
5. From Ilaw, AU=q+ W, property
for adiabatic process 11. Extensive properties depend upon quantity of
q=0, .:. AU= W substance.
.Work involve in adiabatic process is at the 12. In cyclic process AE =0hence q = -W
expense of change in internal energy of the 13. All are facts
system 14. Note that for isothermal PV = constant and so
6. In an isochoric process, AV= 0, hence work B curve represents this process. PV"
done PAV= W=0. So, AE =g+0. Hence, the
constant for adiabatic process (C curve). A is
increase in internal energy will be equal to
isobaric and D is isochoric.
heat absorbed by the system. 15. A,C,D All natural processes are
thermodynamically ireversible.

6.2 First law of Thermodynamics (Heat, Work and Energy)

which AU = 2. One mole of an ideal gas at 25°C expands in
1. A system undergoes a process in
+300 J while absorbing 400 J of heat energy volume from 1.0 L to 4.0 L at constant

and undergoing an expansion against 0.5 bar. temperature. What work (in J) is done if the
What is the change in the volume (in L)? gas expands against vacuum (Pextemal =0)?
2) 5 1) -4.0 x 10² 2) -3.0 x 10
1) 4
3) 2 4) 3 3) -1.0x 10 4) Zero
 Volume-L
3. The work done in
218
0.45
GPCC, Nkl
J/g°C) at 100°C
ergs for the 11. A 10g pieceof iron (C =
expansion of one mole of an ideal gasreversible
from a is dropped into 25g of water (C= 4.2 J g°C) at
volume of 10 litres to 20 litres at 25°C is 27°C. Find temperature of the iron and water
1)-2.303 x 298 x 0.082 log 2 system at thermal equilibrium
2) -298 x 10' x 8.31 x 2.303 1) 30°C 2) 33°C
log 2
3) -2.303 x 298 x 0.082 log 0.5 4)60°C
3) 40°C
4) -8.31x 10' x 12. 2 mole of zinc is dissolved in HCI at 25°C.
2982.303 log 0.5
The work done by a system is 8joule, when The work done in open vessel is
40 joule heat is supplied to it. What is the 1)-2.477 kJ 2) -4.955 kJ
increase in internal energy of system 3) 0.0489 kJ 4) 0.0742 kJ
1) 25 J 2) 30 J 13. 40 J heat is supplied to a gaseous system.
3) 32 J 4) 28J Simultaneously the gas expands against
5. A system has internal energy equal to external pressure l atm by 0.5L. Calculate the
U1, 450
Jof heat is taken out of it and 600 J of work is change in internal energy of system.
done on it. The final energy of the system will 1)-11.60J 2) -10.63J
be
3) +10.63J 4) -11.61 J
1)(U, + 150) 2) (U, + 1050) 14. For isothermal expansion of an ideal gas, the
3)(Uj - 150) 4) (Uj - 1050) correct combination of thermodynamic
6. 8g of helium expand isothermally and parameters will be
reversibly from a volume of 10L to 100L at a 1)AU=0, q = 0, W#0and AH 0
constant temperature of 300K. The work done 2) AU #0, q#0, W0and AH =0
during the expansion is
1) +3.46 kJ 3) AU= 0, q 0, W=0 and AH#0
2) +20 kJ
3) -20 kJ 4) -11.5 kJ 4) AU= 0, q#0, W0 and AH =0
7 When 1 mol of an ideal gas expands reversibly 15. What are q, w and AE if a gas absorbs 200J of
from a volume of 1 dm to 10 dm at a heat and expands from 10 to 20L at 27°C
temperature of 27°C, the work done against a pressure of 1atm?
1)61.57 kJ 2) -5.75 kJ 1) -200J, -1013J, -813J
3) 89.73 kJ 4) 41.57 kJ 2) -200J, 1013J, -1213J
8. 2 moles of an ideal gas expanded isothrmally 3) +200J, -1013J, -813J
and reversibly from 1 lit to 10 lit at 300 K. 4) +200J, 1013J, 1213J
What is the enthalpy change? 16. One mole of a mon0 atomic gas (y 5/3) is
1)4.98 kJ 2) 11.47 kJ mixed with one mole of a diatomic gas
3) -11.47 kJ 4) 0 kJ (r-7/5). The value of for themixture is
9 One mole of a gas absorbs 200J of heat at 1)1.0 2) 2.0
constant volume. Its temperature rises from 3) 0.5 4) 1.5
298K to 308K. The change in internal energy is 17. P-V plot for two gases (assuming ideal) during
1) 200 J 2) -200 J adiabatic processes are given in the plot A and
298
3)200 x 308J 4) 200 x J plot B should correspond respectively to
298 308

10. An ideal gas expands against a constant

external pressure of 2.0 atmosphere from 20
from
litre to 40 litre and absorb 10 kJ of heat A
surrounding. What is the change in internal
energy of the system?
(Given: l atm-litre =101.3J) 1))He and H, 2) H, and He
2) 5948 J
1) 4052 J 3) He and Ne
4) 9940 J 4) Hz and Cl
3) 6042 J
 Volume -l 219 GPCC, Nkl
18. The temperature of an
ideal gas
1) adiabaticexpansion increase in an 29A monoatomic gas is expanded adibatically
from 2L to 10 L at 1atm external pressure
2) isothermal expansion
find U (in atm L)?
3) adiabatic compression 1)-8 2) 0
4) isothermal compression 3) -66.7 4) 58.2
19. During the adiabatic 2NH3, AH is
expansion of an
against atmospheric pressure, the ideal gas 27. For the reaction N, + 3H)
energy will internal equal to
1) AE -RT 2) AE- 2RT
1) increase 2) decrease 4) AE +2RT
3) no change 3)AE + RT
4) not able to say 28. The slopes of isothermal and adiabatic in the
20. The value of AH for
cooling 2 moles of an plot of log P vs log Vare related as
ideal monatomic gas from 125°C to 25 °C at 1) isothermal curve slope = Adiabatic curve
constant pressure will be [given Cp= R) slope
2 2) isothermal curve slope =yx adiabatic curve
1)-250 R 2) -500 R slope
3)S00 R 4) +250 R 3) Adiabatic curve slope Y X isothermal
21. One mole of an ideal gas (Cy = 20 JK mol) curve slope
initially at STP is heated at constant volume to x isothermal
4)Adiabatic curve slope =
twice the initial temperature. For the process, 2
W and q will be curve slope
1) W=0;q=5.46 kJ 29. If the internal energy of an ideal gas decreases
2) W= 0,q=0 by the same amount as the work done by the
3) W=-5,46 kJ ; q=5.46 kJ system, the process 1s
4) W= 5.46 kJ; q =5.46 kJ l) cyclic 2) isothermal
22. The approximate work done during expansion 3) adiabatic 4) isochoric
of a gas from a volume of 4 dm to 6 dm 30. The internal energy of one mole of gas is
against constant pressure of 2 atm is 1)3/2 RT 2) 1/2 KT
1) -608J 2) -405 J 3) 1/2 RT 4) 3/2 KT
3) -304 J 4) -101 J 31. If gas at constant temperature and pressure
expands then its
23. Temperature of l mol of a gas is increased by 1)Internal energy ncreases and then
1Kat constant pressure. Work done is
decreases
1) R 2) 2 R
2) Internal energy increases
R 3)Internal energy remains the sanme
3) 4) 3R
4) Internal energy decreases
24. When a polyatomic gas undergoes an 32: In an isochoric process the increase in internal
adiabatic process, its temperature and volume energy is
are related by equation TV" = constant, the 1)Equal to the heat absorbed
value ofn will be 2) Equal to the heat evolved
1)1.33 2) 0.33 3)Equal to the work done
3) 2.33 4) 1 4) Equal to the sum of the heat absorbed and
25. The molar heat capacity of water at constant work done
pressure, Cp is 75 JK" mol, When 10kJ of 33. One mole of an ideal gas is allowed to expand
heat is supplied to 1kg of water which is free reversibly and adiabatically from
to expand, the increase in temperature of water temperature of 27°C. If the work done during
is the process is 3kJ, then final temperature of
1) 2.4 K 2) 4.8 K the gas is (Cy = 20 J/K)
4) 10 K l)100 K 2) 150 K
3) 3.2 K
3)195 K 4) 255 K
 Volumeel 220 GPCC, Nk
34. A given mass of gas expands from the state A
6
to the state B by three paths 1, 2 and 3 as
shown in the figure. If w W2 and 39
2
I | Calculate work done
W} respectively be the work done by the gas
along three paths then. 1) 12 atm.L 2) 24 atm.L
3) 48 atm.L 4)36 atm.L
40. An ideal gas is taken around the cycle ABCA
as shown in P-V diagram. The net work done
by ideal gas during the cycle is equal to
6P,.B
1) w>W > Ws 2) w <W, < W3
3) wË =W = W; 4) W <W < W
35. The specific heat of a gas at constant volume
is 0.075 cal/g. Predict the atomicity of the gas. A
Molar mass of gas is 40 g mol'.
V Volume 3V,
1) 1 2) 2
3) 3 4) none of these 1) 12 P,V1 2) 6 P;V,
36. One mole of mono atomic ideal gas at TK is 3) 5 P;Vi 4) P,V)
expanded from 1L to 2L adiabatically under a 41. Select the incorrect statement
constant external pressure of 1atm. The final 1) An adiabatic system cannot exchange
temperature of the gas in Kelvin is energy with its surroundings
T 2) A thermodynamic property which is
1) T 2) intensive is additive
3) Work done is zero in an isochoric process
3) T-. 2 4) T+
2 4) A thermodynamic property which is
3R 2R extensive is additive
37. If Wi, W, w; and wW4 for an ideal gas are 42. One mole a mono atomic gas is mixed with
magnitude of work done in isothermal, one mole of a diatomic gas. The value of y for
adiabatic, isobaric and isochoric reversible the mixture is
expansion processes, the correct order will be 1) 1.0 2) 2.0
3) 0.5 4) 1.5
43. One mole each of CaC2, AlC3, MgC3 react
P W3 with H0 in separate open flasks at 25°C.
Numerical value of the work done by the
system is in order
1)CaC, < AlC,< MgC3
WA 2) CaC2 < AlC, = MgC;
3)CaC2 = Mg,C3< AL,C;
1) W; > W2> W3 > W
4)CaC) = Mg,C}= Al4C;
44. The. combination of plots which does not
2) W;>W)> Wi > W
represent isothermal expansion of an ideal gas
3) W3 >W2 > W4 >Wi
4)W3 > WË> W2 >W4
38. For a reversible adiabatic ideal gas expansion A)
dP B)
-is equal to
P 1Nm Vm
dV dy
2) Yy PV
C) D) P
V P
Vm
 GPCC,Nk
221 gas,
Volume-L
is assumed to be a perfect
1) B and D 2) A and D 47. If water vapour, vapourisátion of
3)B and C 4) A andC molar enthalpy change for100°C is 41kJ mol'.
Imol of water at 1I
bar and
45. One mole of gas is heated at constant pressure. changë of. the
The fraction of heat absorbed in doing work is Calculate the internal energy
following process
2)1.!
Y H,Oy ’ H,Og) 2)38 J/mol
1) 38 kJ/mol 4)0.038 kJ/mol
3) y - 1 4) y 3) 42 kJ/mol
given to the gas X in an
46. Two moles of Helium gas expanded 48. When 500 J heat is work doDe comes out as
isobaric process its
isothermally and ireversible at 27°C from 142.8 J. The gas X is
volume 1 dm to 1m' at constant pressure of 2) NH,
1)O2
100 k Pa. Calculate the work done.
3) He
4) SO2
1) 99900 kJ 2) 99900J
3) 34464.65kJ 4) 34464.65 J

Answer Key &Solutions (6.2)

Answer Key
11 12 13.14 15
7. 3 8 10
1234 5 6
4 3
4 4 2 2 2
3 4 2 3 4 2
25 26 27 28 29 30
16 17 18 19 20 2122 23 24
2 1 2 1. 2 3 3
4. 2 3 2 2 1
35"36 37 38 39 40 41 42 43 4445
31-32 3334
3 1 2 2. 1 3 4 2 2 3 2 4 3 1 2
46 47 48
2 1 1

Solutions
1. AU=q +w?" Initial internal energy =Ui
300 = 400 - 0.5 x AV x 100 Heat taken out =450 J
Work done on thesystem = 600 J
AV=2L
.:. Internal-energy=q+w
2. The work done when the gas expands against *-450 +.600 = 150 J
vacuum is zero. .:. Total energy =[U+ 150]
3. W=-2.303 nRTlog 6. W=-2.303 nRT 1log
V
20 100
=-2,303 x] x8.314 x10' x298 log =-2.303 x 8.314 x 10 x 300 log
10 4 10
= -11.5 kJ
= -298 x10' x8.314 x2.303 log 2
7 W= -2.303 nRT log
4, q=40J
w=-8J (work done by the system)
=-2.303 x 1x 8.314 x300 x 10°x log
AE =qtw=40-8 =32 J. =-5.75 KJ
 222
GPCC, NkI
8. Voume-l
AH = AU+ nRAT+ Ifone molc of cachgas mixed
AnRT
For isothermal and reversible expansion R+R
AU= 0, AT =0 C,= 22-2R
2
Here An - 0 =R+ C
since, given system is gas in cylinder type Coe
p(mixture)
'vmixture)
=R+ 2R =3R
system. 3R
Cp(mixture ) C=1.5
.. AH =0 Y(mixture) 2R
at constant volume W =0 Cutmixture)
process PðT
AU=q + W 17. PV = constant for isothermal
is the
constant for adiabatic process sO more
AU=q= 200 Joule
10. AU=q+w value ofy, more is decrease in pressure.
=10 x 1000- 2x (20) x 101.3 = 5948 J 18. During adiabatic compression temperature is
increases.
11. Heat lost by iron + heat gained by waer =0
19. AE =Q+ W
10x 0.45 (T-373) + 25 x 4.2 (T -300) =0
T=303K (or) 30°C 20. T;= 125 C=398 K
12. Zn+2HCI ’znCl,+H2(e) T;= 25'C= 298 K
AH=nCp (Tr- Ti)
Ane =1-0=1
AH=2 x 5 R(298-398)
W=-P. AV=-AngRT =-1x8.314 x298 2
For 2 moles AH=-500 R
-2x8.314x 298 21. W= PAV = Px0=0
W= =4.95S KJ
1000 Q=Cv (AT) =20 x 273 = 5460J = 5.46 kJ.
13. AU =q+w
22. W= -P (V,-V)
AU=?, q=+40 J, w=-Pext. AV
=-2 (6-4) = -4 dm atm
=-1x0.5 =-0.5 L. atm
= -4x 101.3 = -405. 2 J
=-50.63 J
[l dm' atm= 101.3 J]
(:: 1Latm = 101.26 J) 23. PV =RT at TK
Thus, AU= (+40)+(-50.63) = -10.63 J PAV = nRAT = AxRx1
14. In isothermal process
.PAV =R
AT =0
4
AU= 0 24. For polyatomic gas, y ==1.33
3
AH=0

qz0 Y= Cp ,TVY=TY"
Cy
W0 Y-1=n
15. q=+ 200J 1.33 -1n, n= 0.33
w=-PAV= -1x(20- 10)=-10 atm L 25. 4, =n C, AT
=-10 x 101.3J = -1013 J
10000 J = 1000 x
AE =q +t w= (200 - 1013)J= -813J 75
18 (AT), AT =2.4 K
26. Process is adiabatic . O
16. for amono atomic gas C =- R =0
.:. AU=w=-P. AV
for adiatomic gas C,= R =-1(10- 2) atm L
2
= -8atm L
 Volume-I
27. AH = AE + An_RT, An,
223 GPCC, Nkl
=-2 3
R (T; -T)= -
AH= AE- 2RT 2
28. For isothermal process PV= -2
constant T;-T=
log P + log V = log C 3R
log P=-og V + log C 2
Slope of log P vs log V = -1 T; = T
3R
For adiabatic process PV =
constant
log P =y log V = log C 37. P W3
log P =y log V + log C
slope of log P vs log V=y
adiabatic slope =y x-1 WA
=yx isothermal slope
29. AU =0+ W W3> Wi> W2>W4
Adiabatic process Q=0 38. PV= constant, P.y Y,dV + V.dP0
AU = W dP dV
3 p V
30. KE = RT
2 39. W = area under curve
31. We know that internal energy ofa gas depends = (12 - 4) (5- 2)
upon its pressure and temperature. Thus, if a = 24 L - atm
gas expands at constant temperature and 40. Work done Area of the cycle
pressure, then its internal energy remains same
1
32. AE =Q+ W bh
2
Isochoric process W=0

2
(3V-Vi) (6P1 -Pi)
Increase in internal energy’Q=+ve ’ heat
absorbed 1
=,x2VË
2
xSP,
33. W = C, (T2-T) Expansion ’ w=-ve
-3000 = 20 [T;- 300] = SP,Vi
-3000J =20T, -6000 41. Intensive properties are not additive
6000-3000 3000 e.g., density is an intensive property.
T, = 150:K
20 20
Density of mixture of 1lit water with another
34. More the area under the curve, more is the
1lit water is again lgm/ml only
work done
35. C, = 0.075 x 40 =3 cal 42. For monoatomic gas, Cy =R,
2
Cp-Cy =R or Cp -3=2>Cp =5cal
=-=1.66 The gas is monoatomic. diatomic gas, Cy = R
3 2
Cy
36. For an adiabatic process q=0 R+R
2
. AU = W Cimix 2
-=2R
nCv (T; -Ti)= -Pext (Vy-Vi)
CP(mix) = R+Cvimix)=R+ 2R= 3R
xRx(T;
I 2 - T) =-l (2 - 1) Imix
C,P(mix) 3R
-=1.5
2R
Cyimix
 Volume -l 224 GPCC, Nk
43. W AnRT 48. W=pAv
Wc An Given,p = 100k Pa= 10° Pa.
CaCxs) + 2H,0 ’ V,=l dm = 10°m, V,= Im'
Ca(OH)28 + C,H2(9) An =1 W= 10' x (1 -10)J
= 0.999 x 10
Al4Cys+12H,0-»4Al(OH)) +3CHa An=3 .: W=99900 J
Mg,Cs+H,0’ 2Mg(OH)29) +CH,-C=CHe) 47. AH = AU+ An,RT
An = 1
44. For isothermal expansion PVm=K AU=AH -An,RT
=41- (1) (8.314 x 10) (373)
=41-3.108
= 37.9 kJ/mol
48. W=pdv ’ nRdT ----(1)
Vm 4, =nCpdT --2)
45. Fraction of heat absorbed for work done from (1) and (2)
work done
W=nR
total heat absorbed nCp
W

.:. Ch= W
nRAT R
500
nCpAT C C= 142.8 R’ R diatomic > O2
p,m 2
R 1
=1-.

6.3 Thermochemistry (Enthalpies of Reactions)

1. The enthalphy change of a reaction does not 4. Given that C + 0,’CO,AH® =-xkj
depend upon 2C0 + O,’ 2C0,AH =-ykj
1) state of reactants and products the enthalpy of formation of carbon monoxide
2) nature of reactants and products will be

3) different intermediate reactions 1) 2x-y 2)Y-2x

2
4) initial and final enthalpy change of a 2
reaction 3) 2x - y 4) y=2x
5 The species which by definition has zero
2. 3C,H,g) ’ CoHse) ; 4,H° =? (KJ) standard molar enthalpy of formation at 298 K is
If AH° (C,H)), = 230 KJ mol' and 1)Br2(g) 2) Clh(g)
AH° (CçHÙ), = 85 KJ mol 3) H;O(g) 4)CH(g)
1) 205 2) 605. 6. Which of the following reactions defines AH,
3) -605 4) -205
the 1) C(diamond) + Oz(g) ’CO:(g)
3. The heat of formation of the compound in
following reaction is 2) Ha(g) +2 Fz (g) ’ HF(g)
44 kcal
H2g + Cl(g) ’ 2HCI(g) +2) -22 kcal mol 3) N2 (g) + 3H2(g) 2NH3(g)
1)-44 kcal mol'
4) -88 kcal mol:! 4) CO(g) + O:(g) ’ CO2 (g)
3) 11 kcal mol!
 Volume-I 225 GPCC, Nkl
7. The AH? for
CO; (g),CO(g) 14. Which value of heat of formation
indicates
-393.5, -110.5 and -241.8 kJ moland H,0 (g) are that the product is the least stable?
The standard enthalpy respectively. 2) -231.6 Cal
the reaction CO, (g) + change (in kJ mol') for 1) -94 K.Cal
4) +64.8 K.Cal
H(g) ’ COg) + 3) +21.4 KCal
H,0(g)is 15. In the reaction C(s) + O (g)’ CO2 (g) +93.4
1) 524.1
2) +41.2 kcal
3) -262.5
4) -41.2 1) Enthalpy of products is greater than that of
8
The enthalpies
of formation of Al,0, and reactants
Cr;0; are
-1596 kJ and -1134 kJ, 2) Enthalpy of products is less than that of
respectively AH for the reaction 2Al + Cr03
. reactants
’ 2 Cr + Al,0; is 3) Enthalpy of products is same as that of
1)-1365 kJ 2) 2730 kJ reactants
3) -2730 kJ 4) -462 kJ 4) Enthalpy of products is half of that of
9. Xy, X) and y2 are diatomic reactants.
molecules if AH,3, 16. Study the following thermo chemical
AHyy, and AH,, are in the ratio of 2:1:2
and enthalpy of formation of x - y from x; and equations.
y2 0s -100 kJ/mol. The value of AHy-x is A’ B AH =+ 100 kcal

1) 150 kJ/mol B’C AH=-80 kcal

2) 23.92 kJ/mol
3) 100 kJ/mol 4) 400 kJ/mol
The correct order of enthalpies of fomation of
10. Which one of the following has AH; as zero? A, B and C
1) A<B<C 2) A<C<B
1)Brz(g) 2) O;(g)
3) I2 (s) 3) C<A <B 4) B<C<A
4) C(diamond) 17. If combustion of 4 gm of CH, liberates 2.5
11. The enthalpy at 298K of the reaction H,00 > K.Cal, then heat of combustion of CH, is
H;O, +Ozg)
2
is -23.5kcal'mol. The enthalpy 1)-2 K.Cal /mol 2)-10 KCal /mol
3) 8 K.Cal /mol 4) 9 KCal /mol
of formation of H,O20 is 44.8 kcal/mole. The
18. The heat of formation of CO and CO, are
enthalpy of formation of H;O, is -26.4 kCal and -94 kCal, respectively. Heat of
1)-68.3 kcal/mol 2) 68.3 kcal/mol combustion of carbon monoxide will be
3) -93.8 kcal/mol 4) 93.8 kcal/mol 1) +26.4 kcal 2) -67.6 kcal
12. Enthalpy of fornation of two compounds x 3)-120.6 kcal 4) +52.8 kcal
and y are 84 kJ and - 156 kJ respectively.
19/The standard enthalpies of formation of CO;
Which of the following statements is correct (g), H;0(|) and glucose (s) at 2s° C are - 400
1) x is mnore stable than y kJ/mol, -300kJ/mol and -1300 kJ/mol,
2) x is less stable than y
respectively. The standard enthalpy of
3) Both x and y are unstable
combustion per gram of glucose at 25° C is
4)x and yare endothermic compounds 1)+2900 kJ 2) -2900 kJ
13/Calculate the standard enthalpy of reaction for 3) -16.11kJ 4)+16.11 kJ
the following ionicprocess. 20. Determine the enthalpy of the reaction,

2
H + AgCly ’ Ag +H + CI C,Hs(g) + H{g) ’ CçHo(g) + CHg), at
25°C, using the given heat of combustion
Given that : AH=-30360cal mol values under standard conditions.
Compound:
AHr) = 40020cal
Ha(g),CH(g), C;He(g), C(graphite)
1)-9660 cal 2) +9660 cal AH° (kJ/mol) :-285.8, -890.0, -1560.0, -393.0
4)-6560 cal The standard heat of formation of C3 H¡ (g) is
3)+6560 cal
-103 kJ/mol.
 Volume 226
2) 26 days
GPCC, NK
1)-sS kJ 2) -100 kJ 1) 20days
3) -125 kJ 3) 28 days 4) 24 days
4) -110 kJ ethyne i
21. The standard enthalpy of
combustion at 25°C 27. AH for combustion of ethane and
of hydrogen, cyclohexene (C Hio) and -341.1 and -310.0Kcal respectively, which is
cyclohexane (C% Hy2) are -241, better gas welder?
-3920 kJ/ mol respectively. Calculate-3800
the
and
heat
1) ethane 2) ethyne
of 3) Both (1)and (2) 4)Can't be predicted
hydrogenation of cyclohexene.
1)-242 kJ/mole 28. If enthalpy of combustion of the following
2) -222 kJ/mole
3) -121 kJ/mole cyclo alkanes are (values hypothrtical)then
are
4)-400 kJ/mole which cyclo alkane is more stable
22. C) t Ss9)’ CSz0; AH=+117KJ +O,’3CO, +3H,0 AH= -499.8KI
Co) +Og)’ COxg); AH° =-393 KJ +0;’ 4CO, +4H0 AH=-656KJ
-Sss) +O9)-’ SO29); AH° = -297 KJ |+O2- 6CO, + 6H,0 AH=-944.6KJ
The heat of combustion of CS, is 1) cyclo propane 2) cyclohexane
1) -880 KJ 2) +880 KJ 3) cyclo butane 4) all are equal
3) +1104 KJ 29. Heat of reaction for
4) -1104 KJ
23. Consider the reaction at 300K CoH120(s) + 602(g) ’ 6CO,(g) + 6H,0(0)
at constant pressure is -651 Kcal at 17°c
CoHs(0) +Og)
2 ’ 6C02.8) +3H;O0 Calculate the heat of reaction at constant
volume at 17°C.
AH=-3271 kJ
What is AUfor the combustion of 1.5 mole of 1) -554.5 Kcal 2) -651 Kcal
benzene at 27°C 3) -354.5 Kcal 4) -154.5 Kcal
1)-3267.25kJ 2) -4900.88 kJ 30. The heat of combustion of methane in bomb
3) -4906.5 kJ 4) -3274.75 kJ calorimeter was found to be 300 kJ mol' at
24. Heat of combustion of ethanol at constant 28° C. Find heat of combustion at constant
pressure and at temperature TKis found to be pressure in kJ mol!
-q J mol'. Hence, heat of combustion (in J 1)295 2)- 295
mol) of ethanol at the same temperature at
constant volume will be
3),305 4) 305
31. Enthalpies of combustion of CHA, CH, and
1)RT -q 2)-<q +RT)
C,H% are - 890, -1411 and -1560 KJ/mole,
3)q- RT 4) q+ RT
respectively. Which has the highest fuel
25. A schematic representation of enthalpy value?
changes for the reaction Cgraphite + l/2 O2(e) ’
1) CH, 2) CzH6
COe) is given below. The missing value is 3) CH4
graphite +0,(g) 4) Allare same
32. In bomb calorimetry, combustion of benzoic
CO(g) + 1/, 0,(g) acid is often used to determine the heat
-393.5 kJ
-283.0kJ capacity of bomb calorimeter. In a bomb
CO,(e) calorimeter, 1085 g water was taken and
1)+ 10.5 kJ 2)-11.05 kJ combustion of 1 g benzoic acid raised the
3)- 110.5 kJ 4) 10.5J
contain 11.6 kg
temperature by 4.96°C. If heat of combustion
26. A cylinder of gas is assumed to of benzoic acid is 26.42 kJlg,
of butane (C4Hio). If a normal family
needs Calulate the
cylinder will heat capacity of bomb.
20000 kJ of energy per day. The butane I)7.9 x 10 J deg
combustion of 2) 7.9 x 10 J deg"
last: (Given that AH for 3) 7.9 x 10 J deg
is - 2000 kJ) 4) 7.9 x 10² J deg
 Volume-1
33. Calculate the enthalpy change 227
GPCC, Nkl
trans for the cis - 40. Heat of neutralization of a polybasic acid by
HOOCisomerization,
for the reaction. strong monoacidic base is -54.8 kcal mot
COOH What is basicity of the acid?
HOorCc 1) 4 2) 2
(cis) 3) 3 4) 1
(trans) H
The enthalpies of combustion of malic acid 41. The enthalpy of neutralization of HCN by
(cis) and fumaric (trans) are - 1355.16 kJ mol" NaOH is -12.13 kJ mol'. The enthalpy of
and -1334.65 kJacid
mol' ionization of HCN willbe
1)-10.51 kJ
3) 10.51 kJ
respectively.
2) -20.51 kJ 1) 4.519 kJ 2) 45.17 kJ
4. The 4) 20.51 kJ 3) 451.9 kJ 4)45.17 J
products of
thiol (RSH) at 298 combustion
K are
of an aliphatic 42. The heat of neutralization of CH,COOH,
HCOOH, HCN and H,S are -13.2, -13.4, -2.9
1)CO2(g)» H;Otg) and and -3.8 kcal per equivalent respectively.
2)CO2(9), H;O, and SO2g Arrange the acids in increasing order, strength
3) CO20, H,O) and SOg) 1) HCOOH> CH;COOH > H,S > HCN
4) COg H;O, and SO2)
SOg) 2)CH;COOH> HCOOH> H,S> HCN
35. Heat of 3) H,S > HCOOH > CH;COOH> HCN
neutralisation of strong against
strong base is constant and is equalacid 4) HCOOH> H,S > CH;C0OH> HCN
to 43. Calculate amount of heat evolved when 250
1) 13.7 kcal 2) 57 kJ cm' of 0.4M H,SO, is mixed with 500 cm of
3) 5.7 × 10 J 4) Allof the above 0.2M NaOH solution
36. Heat of neutralization of NH,OH and HCI is 1)5,71 kJ 2) 57.1 kJ
1)13.7 kcal/mole 2) <13.7 kca/mole 3) 571 kJ 4) 0.5 kJ
3) >13.7 kcal/mole 4) zero 44. If X K. cal and Y K. cals are the values of
37. A solution of 500 ml. of 0.2 M KOH and 500
ionisation of weak acid (WA) and weak base
ml of 0.2 M HCI is mixed and stirred; the rise
in temperature is TË. The experiment is
(WB) respectively, the enthalpy of neutralisation
of the WA and WB is
repeated using 250 ml each of solution, the 1) 13.7 K.cal
temperature rise is T2. Which of the following 2) -13.7 + (X-Y) K.cal
is true?
3) -13.7 + (X+Y) K.cal
1)TË=T 2) T; = 2T;
4) -13.7 - (X+Y) K.cal
3) T;= 4T; 4) T,=9T
45. The enthalpy of neutralization of a weak acid
38. Calculate the enthalpy change when 50 mL of
1M solution with a strong base is -56.1 kcal
0.01 M Ca (OH), reacts with 25 mL of 0.01 M
HCI . Given that AH° neutralization of a
mol.If the enthalpy ionization of acid is 1.5
kcal mol' and enthalpy, neutralization of the
strong acid and a strong base is 14 kcal mol
2) 3.5 cal strong acid with a strong base is -57.3 kJ eg.
1)14 cal What is the % ionization of the weak acid in
3) 10cal 4) 7.5 cal mol solution (assume the acid is monobasic)
39. Ataparticular temperature 1)25 2) 20
3) 15
Hpa) +OH) ’ H,O, : AH=-57.1kJ 4) 10
46. Equal volumes of 1M HCI and 1M H,SO4 are
The approximate heat evolved when 400 ml of
completely neutralized by IM NaOH solution
0.2 M H,SO4 is mixed with 600 ml of 0.1 M
KOH solution will be separately and x and y kJlequivalent of heat
are liberated, respectively. Which of the
1) 3.426 KJ 2) 13.7 KI
following relations is correct?
3) 5.2 KJ 4) 55 KJ
I) x = 2y 2) x = 3y
3) x = 4y 4) x= 1/2y