Chemical Thermodynamics
Chemical Thermodynamics
Chemical Thermodynamics
It is the study of flow of energy. It encompasses the study of flow Such properties of a system which depends on concentration
of heat as well as mass. and does not depend on the mass or the total number of particles
in the system are categorized as Intensive properties. eg. Pressure,
Density, Reractive Index.
2. THERMODYNAMICS TERMINOLOGY
5. STATE AND PATH FUNCTIONS
2.1 System
Such thermodynamic functions which depend only on the initial
and final states of the system and not on the path followed are
The part of the Universe under observation is called system. called state functions eg. Internal energy, Enthalpy and the
functions which depend on the path followed while changing
2.2 Surrounding from one state to the other are called path functions. eg. work
heat.
The part of the Universe not under observation is called
Surrounding. 6. THERMODYNAMIC EQUILIBRIUM
System + Surrounding = Universe
A system is said to be under thermodynamic equilibrium when
2.3 Types of system none of the state variables are changing and it satisfies the three
equilibriums.
2.3.1 Open System : A system in which both flow of mass and
heat is possible. 6.1 Mechanical Equilibrium
2.3.2 Closed System : A system in which flow of heat is possible
but flow of mass is not possible. There is no mechanical motion and the pressure and the volume
of the system is not changing.
2.3.3 Isolated System : A system in which neither heat nor mass
can flow in or out. 6.2 Thermal Equilibrium
3. STATE OF A SYSTEM There is no flow of heat and the temperature of the system does
not change with time.
The state variables (P, V, T, n) describes the condition of a system.
On changing any one or more of these variables the state of the 6.3 Chemical Equilibrium
system changes.
If any chemical reaction is taking place in the system then the rate
4. PROPERTIES OF SYSTEM of forward reaction is equal to the rate of backward reaction which
means that the overall moles of the system is constant.
All the properties of a system can be categorized into one of the
following two types : 7. INTERNAL ENERGY
4.1 Extensive Properties It is the sum total of the components of energy of the system due
to the internal factors. It is denoted by U (sometimes by E). Since
Such properties of a system which depends on the mass or the the system under observation is an ideal gas thus the internal
total number of particles in the system are categorized as Extensive energy of the system is dependent only on the kinetic energy of
Properties. eg. Total Energy, volume. the gas and therefore is only a function of temperature. U v T.
Since internal energy depends only on temperature thus, it is a
state function.
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180 CHEMICAL THERMODYNAMICS AND ENERGETICS
It is the work done due to the volume changes of the gas. The
There are two methods to alter the internal energy of a system viz.
Heat and work. mathematical expression for the expansion work is w
Pex dV.
8.1 Heat
Always remember, be it expansion or compression we always take
the external pressure as the driving force. For a reversible process,
Heat is the energy transferred due to temperature difference
between the system and the surrounding. On heating, the kinetic Pex | PGAS and w
PGASdV.
energy of the molecules increases and therefore the internal energy
increases. If we draw a process curve between P and V then the work done
is represented by the area covered under the P-V graph as shown
8.2 Work in Fig.
Enthalpy is another thermodynamic function (like internal energy, These processes are the ones in which the temperature is constant
work and heat) which we study in various thermodynamic throughout the process.
processes. It is also a state function like internal energy. It is
'U = 0; 'H = 0
defined as the sum of the energy stored in the system and the
energy used in doing work. Mathematically, H = U + PV. At constant w = 2.303 nRT log10(V2/V1) = 2.303 nRT log10 (P1/P2)
pressure 'H = qp and at constant volume 'U = qV. q = +2.303 nRT log10 (V2/V1) = + 2.303 nRT log10 (P1/P2)
The heat capacity of the system is the amount of heat needed to These processes are the ones in which the heat exchanged with the
raise the temperature of the system by 1C or 1K. surroundings is zero. Such processes are defined by the equation
'T.
C = q/' TVJ1 = constant, TJP1JJ = constant, PVJ = constant.
q=0 w = 'U
14.1 Molar Heat Capacity
'U = nCV'T = (P2V2 P1V1)/(J1). = (nR'T)/(J 1)
The molar heat capacity of a system (CM) is the amount of heat 'H = nCP'T
needed to raise the temperature of one mole gas by 1C or K.
15.3 Isochoric Process
q
CM
n'T
These processes are the ones in which the volume remains constant.
The molar heat capacity of a system at constant pressure (Cp) is Since the change in volume is zero therefore we can say that
the amount of heat needed to raise the temperature of one mole w=0
gas the system by 1C at constant pressure.
'U = nCV'T = qV 'H = nCP'T
'T.
Cp = qp /n'
The molar heat capacity of a system at constant volume (CV) is 15.4 Isobaric Process
the amount of heat needed to raise the temperature of one mole
gas by 1C at constant volume. These are the processes in which the pressure remains constant.
'T.
CV = qV /n' 'V = nR'
w = P' 'T
Thus, we can say that : 'H = nCP'T and 'U = nCV'T and 'U = nCV'T
CP = CV + R.
'H = nCP'T
NOTE
All these processes are happening on a system containing an
ideal gas therefore we can apply PV = nRT at any stage that
we find suitable.
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182 CHEMICAL THERMODYNAMICS AND ENERGETICS
2. Then, Identify every step of the process 3o4 isothermal compression & 4o1 adiabatic compression.
3. Then one by one convert every step into the required graph
bearing in mind critical points like, an expansion process will
remain an expansion process and so on.
It is a generalized form of any thermodynamic process which has 'STOTAL 'SSYSTEM 'SSURROUNDING ! 0
a form PVn = constant where n is a real number. For an isothermal (for a sponataneous change)
process n = 1 and for an adiabatic process n = J. The heat capacity
Thus, In a reversible process the entropy of the Universe remains
of a polytropic process can be calculated using the first law of
thermodynamics and comes out to be : constant i.e. 'STotal = 0
C = CV R/(n 1).
22.1 Entropy changes in a Thermodynamic Process
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A chemical equation which gives us all the information like energy It is the heat released or absorbed when 1 mole of a compound is
changes associated with a chemical reaction and phases of various dissolved in excess of a solvent (water).
reactants and products is called Thermochemical Equation. MgSO4 (s) + H2O (excess) oMg
o 2+ (aq) + SO42 (aq)
All reactions can be categorized into one of the following two
'H0Sol = 91.211 kJ/mol
categories :
25.4 Enthalpy of Hydration
24.1 Endothermic Reactions
It is the energy released or absorbed when 1 mole of anhydrous
Are those chemical reactions which absorb energy. or partially hydrated salt undergoes hydration by the addition of
('H = positive) water of crystallisation. e.g.
CuSO4(s) + 5H2O(l) o CuSO4. 5H2O(s)
24.2 Exothermic Reactions
'HHYD = 78.9 kJ/mol
Are those chemical reactions which release energy.
25.5 Enthalpy of Neutralization
'H = negative)
For a chemical reaction, 'HREACTION = HPRODUCTS HREACTANTS It is the heat released or absorbed when one equivalent of an acid
The change in enthalpy during a chemical reaction occurs due to undergoes neutralisation with one equivalent of a base. e.g.
breaking and making of bonds. H+ (aq) + OH (aq) o H2O (l )
Also, 'H = 'U + 'ngRT. 'HR = 57.3 kJ/mol
Enthalpy change can be calculated for all reactions and is Since enthalpy is a state function thus for a reaction which takes
sometimes called the Heat of Reaction. Lets take a look at various place in steps the net change in enthalpy can be calculated by
types of reactions and enthalpy changes associated with them : adding the enthalpy changes of each step. This is called the Hess
Law.
The entire thermodynamics process of formation of an ionic crystal It is defined as the energy required to convert any substance to
lattice is called Born Haber cycle. An ionic compound is formed gaseous atoms. This is defined per mol of the gaseous atoms. For
from its constituents through a series of steps involving example Heat of atomisation of H will be 218 kJ/mol atoms.
conversion of atoms/molecules into gaseous phase for ion
formation, ionisation and electron gain to form ions and then the 30. RESONANCE ENERGY
reaction of gaseous ions to form solid lattice.
Many compounds exhibit resonance. Due to resonance they exist
28. BOND DISSOCIATION ENTHALPY
in a structure which is different from the expected one and more
stable.
The energy needed to break the bonds of one mole molecules is
called the Bond Dissociation Enthalpy of the substance. It is Resonance energy = 'H0f (actual) 'H0f (calculated)
defined per mol of molecule. eg. Bond dissociation enthalpy of
H2 is 436 kJ/mol
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SOLVED EXAMPLES
20
Example : 1 4754 = 2.303 n 8.314 300 log .
10
Calculate the internal energy change in each of the This given n = 2.75 moles.
following cases :
(i) A system absorbs 15 kJ of heat and does 5 kJ of work. Example : 4
(ii) 5 kJ of work is done on the system and 15 kJ of heat A 5-litre cylinder contained 10 moles of oxygen gas at
is given out by the system. 27oC. Due to sudden leakage through the hole, all the gas
escaped into the atmosphere and the cylinder got empty. If
Sol. (i) Here, q = +15 kJ the atmospheric pressure is 1.0 atmosphere, calculate
w = 5 kJ the work done by the gas. (1 L atm = 101.3 J)
? According to first law of thermodynamics,
'U = q + w = 15 + (5) = 10 kJ Sol. Vinitial = 5L, T = 27oC = 27 + 273 K = 300 K
Thus, internal energy of the system increases by 10 kJ.
nRT 10 u 0.0821 u 300
(ii) Here, w = + 5 kJ Vfinal = 246.3L
P 1.0
q = 5 kJ
'V = 'final Vinitial = 246.3 5 = 241.3 L
? According to first law of thermodynamics,
'U = q + w = 15 + (+ 5) = 10 kJ wexp = P'V = 1 241.3 L atm = 241.3 101.3 J
Thus, the internal energy of the system decreases by 10 kJ. = 24443.7 J.
Example : 2 Example : 5
Calculate w, q and 'U when 0.75 mol of an ideal gas Two moles of an ideal gas initially at 27oC and one
expands isothermally and reversibly at 27oC from a volume atmospheric pressure are compressed isothermally and
of 15 L to 25 L. reversibly till the final pressure of the gas is 10 atm.
Calculate q, w and 'U for the process.
Sol. For isothermal reversible expansion of an ideal gas,
V2 Sol. Here, n = 2 moles T = 27oC = 300 K, P1 = 1 atm, P2 = 10 atm
w = 2.303 nRT log V Putting n = 0.75 mol, V1 = 15 L,
1 P1
V2 = 25 L, T = 27 + 273 = 300 K and R = 8.314 J K1 mol1, w = 2.303 n RT log 2.303 u 2 u 8.314 JK 1 mol1
P2
we get
25 1
w = 2.303 0.75 8.314 300 log 955.5 J
15 300 K log = 11488 J
10
(ve sign represents work of expansion)
For isothermal expansion of an ideal gas, 'U = 0 For isothermal compression of ideal gas, 'U = 0
?'U = q + w gives q = w = + 955.5 J. Further, 'U = q + w ? q = w = 11488 J.
Example : 3 Example : 6
Carbon monoxide is allowed to expand isothermally and
10g of argon gas is compressed isothermally and
reversibly from 10 m3 to 20 m3 at 300 K and work obtained
reversibly at a temperature of 27C from 10L to 5L.
is 4.754 kJ. Calculate the number of moles of carbon
Calculate q, W, ' U and ' H for this process.
monoxide.
R = 2.0 cal K1 mol1. log10 2 = 0.30 Atomic wt. of Ar = 40
V2
Sol. w = 2.303 n RT log V V2
1 Sol. W = 2.303 nRT log10
V1
Example : 7 Example : 9
The state of a mole of an ideal gas changed from state A
A gas present in a cylinder fitted with a frictionless piston (2p, v) through four different processes and finally returns
expands against a constant pressure of 1 atm from a volume to initial State A reversibly as shown below.
of 2 litre to a volume of 6 litre. In doing so, it absorbs
800 J heat from surroundings. Determine increase in
internal energy of process.
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188 CHEMICAL THERMODYNAMICS AND ENERGETICS
?q = w q = + pv 0.5 u 40
T = (0.0821) (2) = 121.8 K.
where q is the heat absorbed in the cylic process.
20
Example : 10 WCA = 2.303 (2) (8.314) (121.8) log10
40
Two mole of a perfect gas undergo the following processes: = 1404.07 J
(a) a reversible isobaric expansion from
Total work, W = 2026.5 + 0 + 1404.07
(1.0 atm, 20.0L) to (1.0 atm, 40.0L).
(b) a reversible isochoric change of state from = 622.43 J
(1.0 atm, 40.0L) to (0.5 atm, 40.0L) For cyclic process : 'U = 0
(c) a reversible isothermal compression from q=w
(0.5 atm, 40.0L) to (1.0 atm, 20.0L).
q = + 622.43 J
(i) sketch with labels each of the processes on the same
P-V diagram. Example : 11
(ii) Calculate the total work (w) and the total heat change
Calculate the amount of work done in each of the following
(q) involved in the above processes.
cases :
(iii) What will be the value of 'U, 'H and 'S for the
overall process ? (i) One mole of an ideal gas contained in a bulb of 10
litre capacity at 1 bar is allowed to enter into an
Sol. The overall is cyclic one, i.e., initial state is regained, thus evacuated bulb of 100 litre capacity.
'U = 0; 'H = 0 and 'S = 0.
(ii) One mole of a gas is allowed to expand from a volume
of 1 litre to a volume of 5 litres against the constant
external pressure of 1 atm (1 litres atm = 101.3 J)
Calculate the internal energy change (' 'U) in each
case if the process were carried out adiabatically.
Example : 12 Example : 14
An ideal gas is originally confined to a volume V1 in an
5.6 dm3 of an unknown gas at S.T.P. required 52.25 J of
insulated container of volume V1 + V2. The remainder of
heat to raise its temperature by 10oC at constant volume.
the container is evacuated. The portion is then removed
Calculate Cv, Cp and J of the gas
and the gas expands to fill the entire container. If the
initial temperature of the gas was T, what is the final
Sol. The 22.4 dm3 of a gas at S.T.P. = 1 mol temperature. Also predict qualitatively, the entropy change
of system, surroundings and the universe.
1
? 5.6 dm3 of the gas at S.T.P. = u 5.6 0.25 mol
22.4
Thus, for 10o rise, 0.25 mol of the gas at constant volume
require heat = 52.25 J
? For 1o rise, 1 mol of the gas at constant volume will
52.25
require heat = 20.9
10 u 0.25 Sol. This is a process of adiabatic free expansion of an ideal
? Cv = 20.9 J K mol 1 1 gas. The internal energy does not change thus the
temperature also stays the same, i.e., the final temperature
Now, Cp = Cv + R = 20.9 J K1 mol1 + 8.314 J K1 mol1 = is still T.
29.214 J K1 mol1
V1 V2
Cp 29.214 'Ssystem = nR ln V1 > 0 ' V 1 + V 2 > V1
? J = 1.4
Cv 20.9
'Ssurr = 0 ' qsurr. = 0
Example : 13 '
'Suniv > 0
q system 340J V2
(i) 'Ssystem Tsystem 403K
-0.84 JK -1 'Ssys = R ln V = R ln 4 = 11.52 JK1
1
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190 CHEMICAL THERMODYNAMICS AND ENERGETICS
1
C6 H 6 A 7 O 2 g
o 6CO 2 g 3H 2 O A 0.2
2 (ii) 200 cm3 of 0.2 M H2SO4 u 200 mole of H2SO4
1000
In this reaction, O2 is the only gaseous reactant and CO2 = 0.04 mole of H2SO4 = 0.08 mole of H+ ions
is the only gaseous product.
0.5
400 cm3 of 0.5 M KOH u 400 mole of KOH =
1 1 3 1000
? 'n g np nr 67 1
2 2 2 0.2 mole of KOH = 0.2 mole of OH ions
Also, we are given 'U (or qv) = 3263.9 kJ mol1 Thus, 0.08 mole of H+ ions will neutralize 0.08 mole of
T = 25oC = 298K OH ions. (out of 0.2 mole of OH ions) to form 0.08
mole of H2O.
8.314
R = 8.314 J K1 mol = kJ K 1 mol 1 Hence, heat evolved = 57.1 0.08 = 4.568 kJ
1000
In case (i), heat produced = 2.284 kJ = 2284 J
'H (or qp) = 'U + 'ng RT = 3263.9 kJ mol1 +
Total volume of the solution = 500 + 200 = 700 mL
C + 2 H2
o CH4,
C(graphite C(diamond)
o 0;
'H = 393.4 + 2 (285.7)
'r Ho = 393.5 (395.4) = + 1.9 kJ
(890.2) kJ mol1 = 74.6 kJ mol1
or C(graphite)
o (diamond) ; 'trans H = + 1.9 kJ Hence, the heat of formation of methane is :
'f H = 74.6 kJ mol1
Example : 19
Example : 21
Calculate the enthalpy of hydration of anhydrous copper
sulphate (CuSO 4) into hydrated copper sulphate Calculate the heat of formation of KCl from the following
(CuSO4.5H2O). Given that the enthalpies of solutions of data :
anhydrous copper sulphate and hydrated copper sulphate
are 66.5 and + 11.7 kJ mol1 respectively (i) KOH (aq) + HCl (aq)
o KCl (aq) + H2O
A , 'H = 57.3 kJ mol1
Sol. We are given
1
(i) CuSO4 (s) + aq (ii) H2 (g) + O 2 g
o H 2O A ,
o CuSO4 (aq) ; 2
1
'sol H1 = 66.5 kJ mol1 'H = 286.2 kJ mol
1 1
(ii) CuSO4.5H2O (s) + aq
o CuSO4 (aq) ; (iii) H 2 g Cl 2 g aq
o HCl aq ,
2 2
'sol H2 = + 11.7 kJ mol1 'H = 164.4 kJ mol1
1 1
We aim at CuSO4 (s) + 5H2O (l)
o CuSO4.5H2O(s) ;
(iv) K (s) O 2 g H 2 g aq o
2 2
'hyd H = ? KOH (aq), 'H = 487.4 kJ mol1
'H = 'H1 'H2 = 66.5 (+11.7) = 78.2 kJ/mol o KCl (aq), 'H = + 18.4 kJ mol1
(v) KCl (s) + aq
1
Example : 20 Sol. We aim at : K(s) + Cl 2 g o KCl s , ' f H ?
2
Calculate the enthalpy of formation of methane, given that In order to get this thermochemical equation, we follow
the enthalpies of combustion of methane, graphite and the following two steps :
hydrogen are 890.2 kJ, 393.4 kJ and 285.7 kJ mol1 Step 1. Adding Eqns. (iii) and (iv) and subtacting Eq. (v).
respectively. we have
1 1
Sol. Remember : Enthalpy of combustion is always negative. K (s) + Cl2 g H 2 g O2 g o KCl s
2 2
We are given : HCl (aq) + KOH (aq) KCl (aq)
'H = 487.4 + (164.4) (18.4) = 670.2 kJ mol1 ... (vii)
o CO2 + 2 H2O, 'H = 890.2 kJ mol1
(i) CH4 + 2O2 Step 2. To cancel out the terms of this equation which do
not appear in the required equation (vi), add eqn. (i) to eqn.
o CO2, 'H = 393.4 kJ mol1
(ii) C + O2 (vii) and subtract eqn. (ii) from their sum. This gives
1 1
(iii) H 2 O2
o H 2 O, 'H 285.7 kJ mol1 K s Cl 2 g
o KCl s ;
2 2
o CH4, 'H = ?
We aim at : C + 2H2 'fH = 670.2 57.3 286.2 = 441.3 kJ
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194 CHEMICAL THERMODYNAMICS AND ENERGETICS
Thus, H2 is a better rocket fuel. ? For production of 0.36 g of glucose, heat absorbed
(b) Writing the reverse of the first reaction, we have 2840
= u 0.36 5.68 kJ
180
1
Al2 O3 s
o 2Al s 1 O 2 g ; 'H 1667.8 kJ mol1
2
Example : 33
Thus, for the reaction given in part (b) of the problem,
'H = + 1667.8 kJ mol1 Calculate the bond energy of CH bond, given that the
heat of formation of CH4, heat of sublimation of carbon
and heat of dissociation of H2 are 74.8, + 719.6 and
Example : 31
435.4 kJ mol1 respectively.
When 1 g liquid naphthalene (C10H8) solidifies. 149 joules
of heat is evolved. Calculate the enthalpy of fusion of Sol. Here, we are given
naphthalene.
C6H12O6 + 6O2(g)
o 6CO2(g) + 6H2O (g) ;
'r H = 2840 kJ mol1
Given that average bond enthalpies are: At 0oC, ice and water are in equilibrium and 'H = 6.00 kJ
mol1 for the process H2O (s) o H2O (l). What will be 'S
CC CH C = O O = O OH and 'G for the conversion of ice to liquid water ?
347 414 741 498 464 kJ mol1
Sol. Since the given process is in equilibrium, 'G = 0
Putting this value in the relationship, 'G = 'H T'S, we
get
Sol. +5 O=Oo3O=C=O+4HOH
'H
0 = 'H T'S or T'S = 'H or 'S =
T
'H = (2eCC + 8eCH + 5eO=O) (6eC=O + 8eOH) We are given 'H = 6.0 kj mol = 6000 J mol and T = 0oC
1 1
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196 CHEMICAL THERMODYNAMICS AND ENERGETICS
Eqn. (ii) + 2 Eqn. (iii) Eqn. (i) gives the required eqn.
Example : 41
with 'H= 393 + 2 (286) ( 726) kJ mol1 =
Calculate the entropy change for the rusting of iron 239 kJ mol1.
according to the reaction :
Example : 43
o 2 Fe2O3 (s), 'Ho = 1648 kJ mol1
4 Fe (s) + 3 O2 (g)
Calculate enthalpy of formation of methane (CH4) from
Given that the standard entropies of Fe, O2 and Fe2O3 are the following data :
27.3, 205.0 and 87.4 J K1 mol1 respectively. Will the
reaction be spontaneous at room temperature (25oC) ? o CO2(g), 'r Ho = 393.5 kJ mol1
(i) C (s) + O2 (g)
Justify your answer with appropriate calculations.
1
(ii) H 2 g O2 g
o H2 O A ,
2
Sol. 'r So = 6 So (Products) 6 So (Reactants) =
'r Ho = 285.8 kJ mol1
o o o
2 S (Fe2O3) [4 S (Fe) + 3 S (O2)]
(iii) CH4 (g) + 2O2 (g)
o CO2 (g) + 2 H2O ( A ),
= 2 87.4 [4 27.3 + 3 205.0] J K1 mol1 = 'r Ho = 890.3 kJ mol1
549.4 J K1 mol1
Sol. o CH4 (g) ; 'f Ho = ?
We aim at : C (s) + 2 H2 (g)
This is the entropy change of the reaction, i.e., system
('Ssystem) Multiplying eqn. (ii) with 2, adding to eqn. (i) and then
subtracting eqn. (iii) from the sum, i.e., operating eqn.
Now, 'rGo = 'r Ho T'r So
(i) + 2 eqn. (ii) eqn. (iii), we get
= 1648000 J mol1 298 K
(549.4 J K1 mol1)
C (s) + 2 H2 (g) CH4 (g) o 0; 'r Ho = 393.5 + 2
(285.8) (890.3) 74.8 kJ mol1
1 15 3
(ii) CO (g) + O 2 g
o (g); 'r Ho = 283.0 kJ moll 'n = 6
2 2 2
327 u 78
Also, 'U per mol = = 3270 kJ
7.8
1
Sol. We aim at : C (s) + o CO g ; ' f Ho
O 2 g ? Now, 'H = 'U + 'nRT
2
3
Subtracting eqn. (ii) from eqn. (i), we get = 3270 + 8.3 300 103
2
1 'H = 3273.735 kJ
C (s) + O 2 g CO g
o 0;
2 Example : 47
'r Ho = 393.5 ( 283.0) = 110.5 kJ mol1 Calculate standard heat of formation of CS2. Given that
standard heat of combustion of C, S and CS2 are 393.3,
1 293.72 and 1108.76 kJ mol1.
or o CO g ; ' r H o
C s O 2 g 110.5 kJ.
2 Sol. We have to find 'H for
? Heat of formation of CO is : 'f Ho = 110.5 kJ mol1 C + 2S oCS2; 'H = ?
Given, C + O2 oCO2; 'H = 393.3 kJ ......... (1)
Example : 45 S + O2 oSO2; 'H = 293.72 kJ ........ (2)
Determine whether or not, it is possible for sodium to CS2 + 3O2 oCO2 + 2SO2 ; 'H = 1108.76 kJ ......... (3)
reduce aluminium oxide to aluminium at 298 K. Given
Multiply Eq. (2) by 2 and add in Eq. (1)
that G 0f of Al2O3 at 298 K = 1582 kJ mol1; G 0f of
Na 2O(s) at 298 K = 377 kJ mol1. C + 2S + 3O2 oCO2 + 2SO2; 'H = 980.74 kJ .......... (4)
Subtract Eq. (3) from Eq. (4)
Sol. The given reaction is :
C + 2S oCS2; 'H = + 128.02 kJ
Al2O3 (s) + 6Na(s) o3Na2O (s) + 2Al(s)
'Hf of CS2 = + 128.02 kJ
Hence, 'G = 3 G 0f (Na2O) G 0f (Al2O3)
Example : 48
(G for Na and Al = 0) Estimate the average SF bond energy in SF6. The standard
= 3 ( 377) ( 1582) = 451 kJ mol 1 heat of formation value of SF6(g), S (g) and F (g) are : 1100,
275 and 80 kJ mol1 respectively.
The reaction cannot occur since 'G (298 K) is positive.
Sol. 'H = esub(s) + 6eF 6eSF
1100 = 275 + 6 (80) 6eSF
eSF = 309.17 kJ/mol
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198 CHEMICAL THERMODYNAMICS AND ENERGETICS
Example : 49 Example : 50
From the following themochemical equations, calculate The standard molar enthalpies of formation of
the enthalpy of formation of cane sugar (C12H22O11) : cyclohexane (l) and benzene (l ) at 25C are 156 and +
(i) C12H22O11 (s) + 12 O2(g) o12 CO2(g) + 11 H2O (l) 49 kJ mol1 respectively. The standard enthalpy of
hydrogenation of cyclohexene (l ) at 25C is 119 kJ
' rH1 = 5644 kJ mol1 mol1. Use these data to estimate the magnitude of the
resonance energy of benzene.
(ii) C (s) + O2 (g) oCO
o 2(g) ' rH2 = 393 kJ mol1
(iii) H2(g) + 1/2 O2(g) oH
o 2O (l) ' rH3 = 286 kJ mol1 Sol. Enthalpy of formation of 3 carbon-carbon double bonds
Sol. AIM : 12C (s) + 11 H2 (g) o C12 H22 O11 (s) 'H = ? 'Hf ( ) 'Hf ( )
+ H2 o ' ; H = 119 kJ
= 152 kJ mol1.
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200 CHEMICAL THERMODYNAMICS AND ENERGETIC
17. Calculate the work done when 1 mol of an ideal gas 573 3 573
(c) 3R An (d) R An
is compressed reversibly from 1 bar to 4 bar at a 473 2 473
constant temperature of 300 K 26. When one mole of an ideal gas is compressed to half
(a) 4.01 kJ (b) 8.02 kJ of its initial volume and simultaneously heated to
(c) 18.02 kJ (d) None of these twice its initial temperature, the change in entropy of
18. 16g of oxygen gas expands isothermally and gas ('S) is :
3 3
reversibly at 300 K from 10 dm to 100 dm . The (a) Cp,m ln2 (b) Cv,m ln2
work done is (in J) (c) R ln2 (d) (Cv,m R) ln2
(a) zero (b) 2875 J
27. One mole of an ideal diatomic gas (Cv = 5 cal) was
(c) + 2875 J (d) infinite
transformed from initial 25C and 1 L to the state
19. The work done during the expansion of a gas from a
3 3 when temperature is 100C and volume 10 L. The
volume of 4dm to 6 dm against a constant external entropy change of the process can be expressed as (R
pressure of 3 atm is = 2 calories/mol/K)
(a) 6J (b) 608 J 298 373
(c) + 304 J (d) 304 J (a) 3An 2 An10 (b) 5An 2 An10
373 298
Entropy & Gibbs Free Energy
373 1 373 1
20. Entropy is a measure of (c) 7 An 2 An (d) 5An 2 An
298 10 298 10
(a) disorder (b) internal energy
28. Which of the following conditions is not favourable
(c) efficiency
(d) useful work done by the system for the feasibility of a process ?
21. The enthalpy of vaporisation of a substance is 8400 J (a) 'H = ve, T'S = ve and T'S <'H
1
mol and its boiling point is 173C. The entropy
(b) 'H = +ve, T'S = +ve and T'S >'H
change for vaporisation is :
1 1 1 1 (c) 'H = ve, T'S = +ve and 'H > T'S
(a) 84 J mol K (b) 21 J mol K
1
(c) 49 J mol K
1
(d) 12 J mol K
1 1 (d) 'H = +ve, T'S = +ve and 'H > T'S
22. The enthalpy of vaporisation of a compound AB at 29. In which of the following cases, the reaction is
1 spontaneous at all temperatures ?
its boiling point (127C) is 6.4 kJ mol . Its entropy
(a) 'H > 0, 'S > 0 (b) 'H < 0, 'S > 0
of vaporisation is :
1 1 (c) 'H < 0, 'S < 0 (d) 'H > 0, 'S < 0
(a) 2.56 kJ mol (b) 16 J mol
3 1 3 1
30. Which of the following is true for the reaction ?
(c) 16 10 J mol (d) 1.6 10 kJ mol ZZX H2O(g) at 100C and 1 atm pressure
H2O(A) YZZ
23. The entropy change for the conversion of 1 mol
of Dtin (at 13C, 1 atm) to 1 mol of Etin (13C, (a) 'S = 0 (b) 'H = T'S
1 (c) 'H = 'U (d) 'H = 0
1 atm), if enthalpy of transition is 2.095 kJ mol
31. A reaction has 'H = 33 kJ and 'S = +58 J/K. This
is :
1 1 1 1 reaction would be :
(a) 7.32 J mol K (b) 14.62 J K mol
1 1
(a) spontaneous below a certain temperature
(c) 56.3 J mol K (d) 0 (b) non-spontaneous at all temperature
24. The following data is known about the melting of a (c) spontaneous above a certain temperature
1 1
compound AB. 'H = 9.2 kJ mol . 'S = 0.008 kJ K (d) spontaneous at all temperature
1
mol . Its melting point is : Thermochemistry
(a) 736 K (b) 1050 K 32. For the reaction :
(c) 1150 K (d) 1150C C s O2 g
o CO2 g
25. The entropy change when two moles of ideal (a) 'H <'U (b) 'H >'U
monoatomic gas is heated from 200C to 300C (c) 'H = 'U (d) 'H = 0
reversibly and isochorically ? 33. For which of the following reactions, 'H is greater
3 300 5 573 than 'U ?
(a) R An (b) R An
2 200 2 273 (a) N2(g) + 3H2(g) o 2NH3(g)
(b) CH2(g) + 2O2(g)
o CO2(g) + 2H2O(l)
(c) PCl5(g)
o PCl3(g) + Cl2(g) (c) 493.7 kJ (d) 297.1 kJ
(d) HCl(aq) + NaOH(aq)
o NaCl(aq) + H2O(aq) 42. When 0.5 g of sulphur is burnt to SO2 4.6 kJ of heat
is liberated. What is the enthalpy of formation of
34. ('U 'H) for the formation of NH3 from N2 and H2 is :
sulphur dioxide ?
(a) 2 RT (b) 2 RT (a) 147.2 kJ (b) +147.2 kJ
1 (c) +294.4 kJ (d) 294.4 kJ
(c) RT (d) RT
2 1
43. The heat of formation of Fe2O3(s) is 824.2 kJ mol .
35. The difference between heats of reaction at constant
pressure and constant volume for the reaction. 'H for the reaction.
2C2H6(l) + 15O2(g) o 12CO2(g) + 6H2O(l) at 2Fe2 O3 s
o 4Fe s 3O2 g is :
25C is (a) 412.1 kJ (b) 1648.4 kJ
(a) 7.43 kJ (b) +3.72 kJ (c) 3296.8 kJ (d) 1648.4 kJ
T
(c) 3.72 kJ (d) 7.43 kJ 44. The 'H for the reaction,
36. Consider the reaction at 300 K 4S(s) + 6O2 (g)
o 4 SO3(g)
H2(g) + Cl2 (g)
o 2HCl(g); 'H = 185 kJ is 1583.2 kJ. Standard enthalpy of formation of
If 2 mole of H2 completely react with 2 mole of Cl2 sulphur trioxide is :
to form HCl. What is 'U for this reaction ? (a) 3166.4 kJ (b) 3166.4 kJ
(a) 0 (b) 185 kJ (c) 395.8 kJ (d) 395.8 kJ
(c) 370 kJ (d) 370 kJ 45. Calculate the heat of formation of PCl5(s) from the
37. The enthalpies of formation of N2 O and NO at 298 K following data :
1 o 2PCl3(l) 'H = 151.8 kcal
2P(s) + 3Cl2(g)
are 82 and 90 kJ mol . The enthalpy of the reaction :
N 2 O g O 2 g o 2NO g PCl3(l) + Cl2(g)
o PCl5(s) 'H = 32.8 kcal
(a) 8 kJ (b) 98 kJ (a) 108.7 kcal (b) 108.7 kcal
(c) 74 kJ (d) 8 kJ (c) 184.6 kcal (d) 184.6 kcal
38. The enthalpies of solution of anhydrous CuSO4 and 46. If S + O2 o SO2 'H = 298.2 kJ
1 1
CuSO4.5H2O are 15.89 and 2.80 k cal mol SO 2 O 2
o SO 3 'H = 98.2 kJ
respectively. The enthalpy of hydration of CuSO4 to 2
CuSO4.5H2O is : SO3 H2 O
o H2SO4 'H = 130.2 kJ
(a) 18.69 kcal (b) 13.09 kcal 1
H 2 O 2 o H2O 'H = 287.3 kJ
(c) 13.09 kcal (d) 18.69 kcal 2
the enthalpy of formation of H2SO4 at 298 K will be
39. If CH3 COOH + OH
o CH3COO + H2O + x kJ
(a) 433.7 kJ (b) 650.3 kJ
+
H + OH
o H2O + y kJ (c) +320.5 kJ (d) 813.9 kJ
The enthalpy change for the reaction : 47. The enthalpies of combustion of carbon and carbon
1
+ monoxide are 393.5 and 283.0 kJ mol
CH3COOH
o CH3COO + H is
respectively. The enthalpy of formation of carbon
(a) x + y (b) x y monoxide is :
(c) y x (d) x y/2 (a) 676.5 kJ (b) 110.5 kJ
40. For the reaction, (c) 110.5 kJ (d) 676.5 kJ
o 2H 2 g O 2 g 'H = 571.6 KJ
2H 2 O g 48. Which of the following pairs has heat of
neutralisation equal to 57.1 kJ ?
'f HT of water is : (a) HNO3,KOH (b)HCl, NH4OH
(a) 285.8 kJ (b) 285.8 kJ (c) H2SO4,NH4OH (d) CH3COOH,NaOH
(c) 1143.2 kJ (d) 1143.2 kJ 49. Which of the following neutralisation reactions is
41. 'H for the reaction, most exothermic ?
1 (a) HCl and NaOH (b) HCN and NaOH
SO 2 g O 2 g YZZ ZZX SO3 g 'H = 98.3 kJ
2 (c) HCl and NH4OH (d) CH3COOH and NH4OH
If the enthalpy of formation of SO3(g) is 395.4 kJ 50. The enthalpy of neutralisation of HCl by NaOH is
1
then the enthalpy of formation of SO2(g) is : 57.1 kJ and that of HCN by NaOH is 12.1 kJ mol .
(a) 297.1 kJ (b) 493.7 kJ The enthalpy of ionization of HCN is :
(a) 69.2 kJ (b) 45.0 kJ
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202 CHEMICAL THERMODYNAMICS AND ENERGETIC
(c) 69.2 kJ (d) 45.0 kJ (a) 260 k cal/mole (b) 180 k cal/mole
51. For the reaction at 300 K (c) 130 k cal/mole (d) 80 k cal/mole
A(g) + B(g) o C(g) 59. For the reaction of one mole of zinc dust with one
'U = 3.0 kcal 'S = 10.0 cal/K mole of sulphuric acid in a bomb calorimeter, 'E and
1 1 W corresponds to
(R | 2 cal mol K )
'G is : (a) 'E < 0, W = 0 (b) 'E = 0, W < 0
(a) 600 cal (b) 3600 cal (c) 'E > 0, W = 0 (d) 'E = 0, W > 0
(c) 2400 cal (d) 3000 cal 60. The bond energies C C, C = C, H H and C H
52. The standard enthalpies of formation of HCl(g), H(g) linkages are 350, 600, 400 and 410 kJ/mol
1 respectively. The heat of hydrogenation of ethylene
and Cl(g) are 92.2, 217.7 and 121.4 kJ mol is
respectively. The bond dissociation energy of HCl is: 1 1
(a) 170 kJ mol (b) 260 kJ mol
(a) +431.3 kJ (b) 236.9 kJ 1 1
(c) 431.3 kJ (d) 339.1 kJ (c) 400 kJ mol (d) 450 kJ mol
53. The enthalpy changes at 25C in successive breaking 61. The standard heats of formation of CH4, H2O and
of OH bonds of water are :
1
CH3OH are 76, 242 and 266 kJ/mol respectively.
H2O(g)
o H(g) + OH(g) 'H = 498 kJ mol The enthalpy change for the following reaction is
1
o H(g) + O(g) 'H = 428 kJ mol
OH(g) CH3OH (l) + H2(g) o CH4(g) + H2O (l)
the bond enthalpy of the OH bond is : (a) 4 kJ/mol (b) 556 kJ/mol
1 1
(a) 498 kJ mol (b) 463 kJ mol (c) 318 kJ/mol (d) 52 kJ/mol
(c) 428 kJ mol
1
(d) 70 kJ mol
1 62. Which of the following reaction defines 'H of ?
54. Calculate the heat of the reaction (a) C (diamond) O 2 (g)
o CO 2 (g)
CH2 = CH2(g) + H2(g)
o CH3CH3(g) 1 1
(b) H 2 (g) F2 (g) o HF(g)
given that bond energy of C C, C = C, C H and 2 2
H H is 80, 145, 98 and 103 kcal. (c) N 2 (g) 3H 2 (g)
o 2NH 3 (g)
1 1 1
(a) 28 kcal mol (b) 5.6 kcal mol (d) CO(g) O2 (g) o CO 2 (g)
1 1 2
(c) 2.8 kcal mol (d) 56 kcal mol
63. The heat of combustion of solid benzoic acid at
55. The enthalpy change for the following reaction is 368
constant volume is 321.30 kJ at 27C. The heat of
kJ. Calculate the average OF bond energy.
combustion at constant pressure is
OF2 (g) o O(g) 2F(g) (a) 321.30 300 R (b) 321.30 + 300 R
(a) 184 kJ/mol (b) 368 kJ/mol (c) 321.30 150 R (d) 321.30 + 900 R
(c) 536 kJ/mol (d) 736 kJ/mol 64. ' H for the reaction,
56. The enthalpy change for the reaction, C(graphite) 2H 2 (g)
o CH 4 (g) at 298 K
C2H6(g) o 2C(g) + 6H(g) is X kJ. The bond energy
and 1 atm is 17900 cal. The 'E for the above
of CH bond is: conversion would be
X X (a) 17900 cal (b) 17900 cal
(a) (b)
2 3 (c) 17308 cal (d) 17308 cal
X 65. If 150 kJ of energy is needed for muscular work to
(c) (d) data insufficient
6 walk a distance of one km, then how much of glucose
o
57. Based on the values of B.E. given, 'fH of N2H4(g) is: one has to consume to walk a distance of 5 km,
1 1 provided only 30% of energy is available for
Given: NN = 159 kJ mol ; HH = 436 kJ mol muscular work. (The enthalpy of combustion of
1 1
NN = 941 kJ mol , NH = 398 kJ mol 1
1 1
glucose is 3000 kJ mol is)
(a) 711 kJ mol (b) 62 kJ mol (a) 75 g (b) 30 g
1 1
(c) 98 kJ mol (d) 711 kJ mol (c) 180 g (d) 150 g
58. The dissociation energy of CH4 and C2H6 are 66. For the reaction,
respectively 360 and 620 kcal/mole. The bond 2H 2 (g) O 2 (g)
o 2H 2 O(g); 'H 573.2 kJ
energy of CC is The heat of decomposition of water per mole is
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204 CHEMICAL THERMODYNAMICS AND ENERGETIC
21. 'S will be highest for the reaction (AIIMS 1994) (d) C(diamond)o C(graphite).
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206 CHEMICAL THERMODYNAMICS AND ENERGETIC
32. 1 mole of ice is converted to liquid at 273 K ; H2O (s) 40. Heat of neutralisation of a strong acid and a strong
and H2O (l ) have entropies 38.20 and 60.03 J mol1 base is nearly equal to (AIIMS 1988)
deg1. Enthalpy change in the conversion will be (a) 10 kJ/mole (b) 10 Cal/mole
47. H2 (g) + I2 (g) o2 HI (g) ; 'H = 12.40 kcal. 55. At constant T and P which one of the following
According to this reaction heat of formation of HI statements is correct for the reaction ?
will be (PMT 1990) S8(s) + 8 O2 (g) o 8 SO2 (g) (PMT 1993)
(a) 12.4 kcal (b) 12.4 kcal
(a) 'H <'E (b) 'H = 'E
(c) 6.20 kcal (d) 6.20 kcal.
(c) 'H >'E (d) 'H is independent
48. Equal volumes of molar hydrochloric acid and
of the physical state of the reactants.
sulphuric acid are neutralized by dil. NaOH solution
and x kcal and y kcal of heat are liberated 56. Consider the following reaction occurring in an
respectively. Which of the following is true ? automobile 2 C8H18 (g) + 25 O2 (g) o 16 CO2 + 18
(PMT 1994) H2O (g) the sign of 'H, 'S and 'G would be
1 (PMT 1994)
(a) x = y (b) x = y
2 (a) +, , + (b) , +,
(c) x = 2 y (d) None of these.
(c) , +, + (d) +, +, .
49. Which of the following values of heat of formation
57. Heat of neutralisation of strong acid against strong
indicates that the product is least stable ?
base is constant and is equal to (PMT 1993)
(PMT 1991)
(a) 13.7 kcal (b) 57 kJ
(a) 94 kcal (b) 231.6 kcal
4
(c) 5.7 10 J (d) All of the above.
(c) + 21.4 kcal (d) + 64.8 kcal.
50. In which of the following neutralization reaction, the 58. When water is added to quick lime, the reaction is
heat of neutralisation will be highest? (PMT 1989,91) (PMT 1995)
(a) NH4OH and H2SO4 (a) explosive (b) endothermic
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208 CHEMICAL THERMODYNAMICS AND ENERGETIC
63. Given that C + O2o CO2'H0 = x kJ 70. The enthalpy of formation for C2H4(g), CO2(g) and
2 CO + O2o 2 CO2'H = y kJ0 H2O (l ) at 25C and 1 atm pressure are 52, 394 and
the enthalpy of formation of carbon monoxide will be 286 kJ mol1 respectively. The enthalpy of
(PMT 1997) combustion of C2H4 (g) will be (PMT 1995)
2x y y 2x (a) + 1412 kJ mol1 (b) 1412 kJ mol1
(a) (b)
2 2 (c) + 141.2 kJ mol1 (d) 141.2 kJ mol1.
(c) 2x y (d) y = 2x. 71. The heat of combustion of benzene at 27C found by
64. The neutralisation of a strong acid by a strong base bomb calorimeter i.e. for the reaction
liberates and amount of energy per mole of H+
C6H6(l ) + 7 1 O2(g) o 6 CO2 (g) + 3 H2O (l ) is 780
(BHU 1998) 2
(a) depends upon which acid and base are involved kcal mol1. The heat evolved on burning 39 g of
benzene in an open vessel will be (PMT 2001)
(b) depends upon the temperature at which the
(a) 390 kcal (b) 780.9 kcal
reaction takes place
(c) 390.45 kcal (d) 780 kcal.
(c) depends upon which catalyst is used
72. If S + O2o SO2, 'H = 298.2 kJ
(d) is always the same.
1
65. Equal volumes of methanoic acid and sodium SO 2 O 2 o SO3 , 'H = 98.7 kJ
2
hydroxide are mixed. If x is the heat of formation of
SO3 + H2O o H2SO4, 'H = 130.2 kJ
water, then heat evolved on neutralisation is
1
(BHU 1998) H2 O2 o H2O, 'H = 287.3 kJ.
2
(a) more than x (b) equal to x
Then the enthalpy of formation of H2SO4 at 298K
(c) less than x (d) twice x.
will be (DPMT 1994)
3
66. S + O 2 o SO3 + 2x kcal (a) 814.4 kJ (b) + 320.5 kJ
2
(c) 650.3 kJ (d) 933.7 kJ
1
SO 2 O 2 o SO 3 y kcal 73. H2 + 1/2 O2o H2O ; 'H = 68 kcal (CPMT 1988)
2
K + H2O + aq o KOH (aq) + 1/2 H2; 'H = 48 kcal
Find out the heat of formation of SO2 (PMT 1999)
KOH + aq o KOH (aq); 'H = 14 kcal
(a) (y 2x) (b) (2x + y)
From the above data, the standard heat of formation
(c) (x + y) (d) 2x/y.
of KOH in kcal is :
67. For the reaction
(a) 68 + 48 14 (b) 68 48 + 14
C3H8 (g) + 5 O2(g) o3 CO2 (g) + 4 H2O (l ) at (c) 68 48 + 14 (d) 68 + 48 + 14.
constant temperature, 'H 'E is 74. The enthalpies of combustion of carbon and carbon
(CBSE Med. 2003) monoxide are 390 kJ mol1 and 278 kJ mol1
(a) + RT (b) 3 RT respectively. The enthalpy of formation of carbon
(c) + 3 RT (d) RT monoxide is (BHU 1994)
68. For which one of the following equations is 'Hreaction (a) 668 kJ mol1 (b) 112 kJ mol1
(c) 112 kJ mol1 (d) 668 kJ mol1
equal to 'Hf for the product ? (CBSE Med. 2003)
75. C + O2o CO2, 'H = x
(a) N2 (g) + O3(g) o N2O3(g) 1
CO O 2 o CO 2 , 'H y
(b) CH4(g) + 2 Cl2 (g) o CH2Cl2 (l ) + 2 HCl (g) 2
then 'Hf for CO will be (DPMT 2002)
(c) Xe (g) + 2 F2 (g) o XeF4(g)
(a) 2x + y (b) x y
(d) 2 CO (g) + O2 (g) o 2 CO2 (g) (c) y 2x (d) y x
69. In which of the following process of neutralisation 76. The amount of energy released when 20 ml of 0.5 M
magnitude of 'Hneutralisation is less than that of 'Hionization NaOH are mixed with 100 mL of 0.1 M HCl is x kJ.
of water ? (BHU 2003) The heat of neutralisation (in kJ mol1) is
(a) HCl + NaOH (b) H2SO4 + NaOH (PMT 2002)
(c) CH3COOH + NaOH (d) HClO4 + KOH (a) 100 x (b) 50x
(c) + 100 x (d) + 50x
77. Heat of neutralisation for the reaction 84. If 'H0f for H2O2 and H2O are 188 kJ/mole and
NaOH + HCl o NaCl + H2O 286 kJ/mole, what will be the enthalpy change of
is 57.1 kJ mol1. What will be the heat released when the reaction 2 H2O2 (l ) o 2 H2O (l ) + O2 (g) ?
0.25 mole of NaOH reacts with 0.25 mole of HCl ?
(PMT 1992)
(PMT 1990)
(a) 196 kJ/mole (b) 146 kJ/mole
(a) 22.5 kJ mol1 (b) 57.1 kJ mol1
1
(c) 494 kJ/mole (d) 98 kJ/mole.
(c) 14.3 kJ mol (d) 28.6 kJ mol1.
85. Considering the following reactions,
78. Enthalpy of neutralisation of HCl with NaOH is x.
1
The heat evolved when 500 mL of 2 NHCl are mixed C O 2 o CO 'H 26.4 K.
with 250 ml of 4 N NaOH will be (AFMC 2002) 2
1
(a) 500x (b) 100x H 2 O 2 o H 2 O (l ) 'H = 57.8 kcal,
2
(c) x (d) 10x 'H for the reaction
79. The enthalpy of dissolution of BaCl2 (s) and H2O + C o H2 + CO is (PMT 1994)
BaCl2.2H2O (s) are 20.6 and 8.8 kJ mol1 (a) 62.8 kcal (b) 31.4 kcal
respectively. The enthalpy of hydration for (c) 31.4 kcal (d) 84.2 kcal.
BaCl2(s) + 2 H2O o BaCl2.2H2O (s) is (PMT 1994) 86. Given :
1
(a) 29.4 kJ (b) 29.4 kJ C (graphite) O 2 (g) o CO (g); 'H = 110.5 kJ
2
(c) 11.8 kJ (d) 38.2 kJ. 1
CO (g) O2 (g) o CO 2 (g); 'H = 283.2 kJ
80. The heats of combustion of rhombic and monoclinic 2
sulphur are respectively 70960 and 71030 calories. The heat of reaction for
What will be the heat of conversion of rhombic C (graphite) + O2 (g) o CO2 (g) will be
sulphur to monoclinic ? (PMT 1988) (PMT 1989)
(a) 70960 calories (b) 71030 calories (a) 393.7 kJ (b) + 393.7 kJ
(c) 70 calories (d) + 70 calories. (c) 172.2 kJ (d) + 172.2 kJ
81. 'Hf of graphite is 0.23 kJ/mole and 'Hf of diamond 87. Heat of combustion 'H for C (s), H2(g) and
is 1.896 kJ/mol. 'Htransition from graphite to diamond CH4 (g) are 94, 68 and 213 kcal/mol. Then 'H
is (BHU 2003) for C(s) + 2H2(g) o CH4(g) is (PMT 2002)
(a) 1.66 kJ/mol (b) 2.1 kJ/mole (a) 17 kcal (b) 111 kcal
(c) 2.33 kJ/mole (d) 1.5 kJ/mole (c) 170 kcal (d) 85 kcal
82. The enthalpies of formation of N2O and NO are 82 88. The enthalpy changes at 298 K in successive breaking
and 90 kJ/mole respectively. The enthalpy of the of OH bonds of HOH are
reaction
H2O (g) o H (g) + OH (g), 'H = 498 kJ mol1
2 N2O (g) + O2 (g) o 4 NO (g) is equal to
OH (g) o H (g) + O (g), 'H = 428 kJ mol1
(PMT 1991)
The bond enthalpy of the OH bond is (PMT 1994)
(a) 8 kJ (b) 88 kJ
(a) 498 kJ mol1 (b) 463 kJ mol1
(c) 16 kJ (d) 196 kJ.
83. Based on the following thermochemical equations (c) 428 kJ mol1 (d) 70 kJ mol1
H2O (g) + C (s) o CO (g) + H2(g); 'H = 131 kJ 89. The bond energy of an OH bond is 109 kcal mol1.
When a mole of water is formed (PMT 1994)
1
CO (g) O 2 (g) o CO 2 (g); 'H = 282 kJ (a) 218 kcal is released (b) 109 kcal is released
2
1 (c) 218 kcal is absorbed (d) 109 kcal is absorbed.
H 2 (g) O 2 (g) o H 2 O (g); 'H = 242 kJ
2 90. Energy required to dissociate 4 g of gaseous
C (s) + O2 (g) o CO2(g); 'H = X kJ, hydrogen into free gaseous atoms is 208 kcal at 25C.
the value of X will be (PMT 1992) The bond energy of HH bond will be (CPMT 1989)
(a) 393 kJ (b) 655 kJ (a) 104 kcal (b) 10.4 kcal
(c) + 393 kJ (d) + 655 kJ. (c) 1040 kcal (d) 104 kcal.
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210 CHEMICAL THERMODYNAMICS AND ENERGETIC
91. Given the reaction at 1240 K and 1 atm.CaCO3 (s) o (b) C(s) 2H 2 O(g) o 2H 2 (g) CO 2 (g)
CaO (s) + CO2 (g) (c) PCl5 (g) o PCl3 (g) Cl2 (g)
(d) 2CO(g) O 2 (g) o 2CO 2 (g)
'H = 176 kJ/mol, the 'E equals (BHU 1993)
98. The enthalpy change ('H) for the reaction,
(a) 160.0 kJ (b) 165.6 kJ
N 2 (g) 3H 2 (g) o 2NH 3 (g)
(c) 186.4 kJ (d) 180.0 kJ. is 92.38 kJ at 298 K. The internal energy change
92. The latent heat of vaporisation of a liquid at 500 K ' U at 298 K is (AIIMS 2007)
and 1 atm. pressure is 10.0 kcal/mol. What will be the (a) 92.38 kJ (b) 87.42 kJ
change in internal energy of 3 moles of the liquid at
(c) 97.34 kJ (d) 89.9 kJ
the same temperature and pressure ? (PMT 1994)
99. The enthalpy of hydrogenation of cyclohexene is
(a) 27.0 kcal (b) 13.0 kcal
119.5 kJ mol1. If resonance energy of benzene is
(c) 27.0 kcal (d) 13.0 kcal. 150.4 kJ mol1, its enthalpy of hydrogenation would
93. Given the following entropy values (in JK1 mol1) at be (AIIMS 2007)
298 K and 1 atm : H2(g) : 130.6, Cl2 (g) : 223.0 and (a) 208.1 kJ mol1 (b) 269.9 kJ mol1
HCl (g) : 186.7. The entropy change (in JK mol1) for (c) 358.5 kJ mol1 (d) 508.9 kJ mol1
the reaction
100. One mole of methanol when burnt in O2, gives out
H2 (g) + Cl2 (g) o 2 HCl (g) is (PMT 1996)
723 kJ mol1 heat. If one mole of O2 is used, what
(a) + 540.3 (b) + 727.0 will be the amount of heat evolved? (AIIMS 2007)
(c) 166.9 (d) 19.8. (a) 723 kJ (b) 924 kJ
94. One gram sample of NH4NO3 is decomposed in a (c) 482 kJ (d) 241 kJ
bomb calorimeter. The temperature of the calorimeter 101. What will be the heat of formation of methane, if
increases by 6.12 K. The heat capacity of the system the heat of combustion of carbon is -x kJ, heat of
is 1.23 kJ/g/deg. What is the molar heat of formation of water is y kJ and heat of
decomposition for NH4NO3 ? (AIIMS 2003) combustion of methane is -z kJ? (AIIMS 2008)
(a) 7.53 kJ/mol (b) 398.1 kJ/mol (a) (xy+z) kJ (b) (zx+y) kJ
(c) 16.1 kJ/mol (d) 602 kJ/mol (c) (x2yz) kJ (d) (x2y+z) kJ
95. How much energy is released when 6 moles of 102. Enthalpy of combustion of methane and ethane are
octane is burnt in air? Given 'Hof for CO2(g), 210 kcal/mol and 368 kcal/mol respectively. The
H2O(g) and C8H18 (A ) respectively are 490, 240 enthalpy of combustion of decane is (AIIMS 2009)
and +160 J/mol (AIIMS 2004) (a) 158 kcal (b) 1632 kcal
(a) 6.2 kJ (b) 37.4 kJ (c) 1700 kcal (d) Data is incomplete
(c) 35.5 kJ (d) 20.0 kJ 103. The heat liberated when 1.89 g of benzoic acid is
96. 'H (298 K) of methanol is given by the chemical
o burnt in a bomb calorimeter at 25oC increases the
f
temperature of 18.94 kg of water by 0.632oC. If the
equation, (AIIMS 2005)
specific heat of water at 25oC is 0.998 cal/g-deg,
1 the value of the heat of combustion of benzoic acid
(a) CH 4 (g) O 2 (g) o CH 3OH(g)
2 is (AFMC 2010)
1
(b) C(graphite) O 2 (g) 2H 2 (g) o CH 3 OH(A) (a) 881.1 kcal (b) 771.4 kcal
2
(c) 981.1 kcal (d) 871.2 kcal
1
(c) C(diamond) O 2 (g) 2H 2 (g) o CH 3 OH(A ) 104. Enthalpy change for the reaction, 4H(g) o 2H 2 (g)
2
(d) CO(g) 2H 2 (g) o CH 3 OH(A ) is 869.5 kJ. The dissociation energy of HH
97. Assume each reaction is carried out in an open bond is (CBSE AIPMT 2011)
container. For which reaction will ' H = 'E ? (a) +217.4 kJ (b) 434.8 kJ
(CBSE AIPMT 2006) (c) 869.6 kJ (d) +434.8 kJ
(a) H 2 (g) Br2 (g) o 2HBr(g)
ANSWER KEY
EXERCISE 1 : BASIC OBJECTIVE QUESTIONS
1. (a) 2. (d) 3. (a) 4. (a) 5. (b) 6. (d) 7. (c) 8. (b) 9. (a) 10. (c)
11. (a) 12. (a) 13. (b) 14. (b) 15. (d) 16. (a) 17. (d) 18. (b) 19. (b) 20. (a)
21. (a) 22. (b) 23. (a) 24. (c) 25. (c) 26. (d) 27. (b) 28. (d) 29. (b) 30. (b)
31. (d) 32. (c) 33. (c) 34. (c) 35. (a) 36. (d) 37. (b) 38. (a) 39. (c) 40. (b)
41. (a) 42. (d) 43. (d) 44. (c) 45. (a) 46. (d) 47. (c) 48. (a) 49. (a) 50. (d)
51. (a) 52. (a) 53. (b) 54. (a) 55. (a) 56. (d) 57. (b) 58. (d) 59. (a) 60. (a)
61. (d) 62. (b) 63. (c) 64. (d) 65. (d) 66. (a)
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