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NOTE: PART 2 CONTAINS QUESTIONS FROM ENTROPY AND FREE ENERGY Prepared by V. Aditya vardhan
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CHEMICAL THERMODYNAMICS (PART-I)
IIT-JEE
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1) Open systems can exchange both energy and matter with its surroundings.
2) Closed systems can only exchange energy and do not exchange matter with its surroundings.
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3) Isolated systems can exchange energy and matter with its surroundings.
4) None.
3) Which of the following is not an intensive property?
1) Entropy 2) Density 3) Temperature 4) Pressure
4) Which of the following is an extensive property?
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1) Entropy 2) Enthalpy 3) Volume 4) All
H
5) Extensive properties, out of a) boiling point, b) viscosity, c) p , d) emf of a cell and e) molar heat
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capacity; are
1) a, b & c 2) b & e 3) c & e 4) None
6) Which of the following is not a state function?
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1) dT = 0 2) dU = 0 3) q 0 4) All
Note: In an adiabatic process, there is no exchange of heat between system and surroundings. Hence dq = 0 and dU = w.
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However there is change in temperature and internal energy during this process.
9) In which of the following processes, dT =0?
1) Adiabatic process 2) Isobaric process 3) Isothermal process 4) Isochoric process
10) In an isochoric process,
1) dT = 0 2) dP = 0 3) dV = 0 4) dH = 0
Note: in isochoric (dV=0) and isobaric (dP=0) processes, the pressure-volume work is always zero.
11) In a cyclic process,
1) dU = 0 2) dH = 0 3) dT = 0 4) All
12) If the systems A and B are in thermal equilibrium with system C, then system A is also in thermal
equilibrium with system B. In thermodynamics, this statement is known as
1) 1st law 2) 2nd law 3) 3rd law 4) zeroeth law
13) Thermos flask is an example of
1) Closed system 2) Open system 3) Isolated system 4) All
14) The correct statement about isothermal process is
1) dT = 0 2) dU = 0 3) q = -w 4) All
15) The statement which is not true according to 1st law of thermodynamics is
1) Energy can neither be created nor destroyed although it can be changed from one form to an-
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other.
2) The total energy of the universe is constant.
3) The change in the internal energy of a closed system is equal to the sum of heat lost or absorbed by
the system and work either done by the system or done on the system
4) The change in internal energy of a system is zero in all the processes
16) The work done during the free expansion of an ideal gas is equal to
1) Pext 2) dV 3) dU 4) zero
17) Which of the following is true about isothermal free expansion of a gas?
1) dU = 0 2) dT = 0 3) PextdV = 0 4) All
18) The work done during isothermal irreversible change will be given by
Vf Vf
1) -Pext(Vf-Vi) 2) 2.303nRT log 3) nRT log 4) zero
Vi Vi
Note: In the irreversible process, the work is done against constant external pressure which differs largely from the internal
pressure.
19) The work done during an isothermal reversible change will be given by
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Vf Vf
1) -Pext(Vf-Vi) 2) 2.303nRT log 3) nRT log 4) zero
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Vi Vi
Note: In case of reversible process, the internal pressure is almost equal to the external pressure. This internal pressure is
given by nRT / V.
20) Two litres of an ideal gas at a pressure of 10 atm expands isothermally into vacuum until its total
volume becomes 100 litres.The amount of heat absorbed in the expansion is
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1) 2.303 J 2) 100 J 3) 90 J 4) None
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Note: As the process is isothermal, q=-w=PdV; And as the expansion is done against zero pressure(Pext=0), the work done as
well as the heat absorbed will be zero.
21) Which of the following statements is true
1) The work done in reversible expansion is less than the work done in irreversible expansion.
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2) The work done in reversible expansion is equal to the work done in irreversible expansion.
3) The work done in reversible expansion is greater than the work done in irreversible expansion.
4) All.
Note: But in case of compression, |wrev| < |wirrev|
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22) Ten litres of an ideal gas at a pressure of 10 atm expands isothermally against a constant pressure of
1 atm. until its total volume becomes 100 litres.The work done in the expansion is
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28) 25 L of an ideal gas is compressed isothermally under constant atmospheric pressure until the vol-
ume becomes 5 L. The change in internal energy is
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1) 20 J 2) -2026.5 J 3) +2026 J 4) 0 J
29) There is a balloon of given volume, V1, containing a gas at temperature, T1. When the balloon is
placed in a colder room at temperature, T2, the balloon’s temperature starts to drop. What are the
signs of the system’s q, w, and E for this process?
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heated to double its temperature. The change in internal energy dU will be equal to
1) +w 2) +q 3) -w 4) -q
Note: As the process is isochoric, the change in internal energy is only due to exchange of heat
dU = qv
31) An ideal gas at 10 atm pressure and occupying 0.1 L is expanded to 1.1 L by supplying 101.325 J
of heat against constant atmospheric pressure irreversibly. The change in the temperature of the gas
during this process is
1) 10 K 2) 1.1 K 3) 1K 4) No change
Hint: dU = q+w = 101.325 J + (-101.325 J) = 0
32) A gas is allowed to expand at constant temperature from a volume of 1.0 L to 10.1 L against an
external pressure of 0.50 atm. If the gas absorbs 250 J of heat from the surroundings, what are the
values of q, w, and E respectively?
1) 250 J, -461 J & -211 J 2) -250 J, -461 J & -711 J
3) 250 J, -461 J & -711 J 4) 250 J, -4.55 J & 245 J
33) In a process, 800 J of heat is absorbed by a system and 350 J of work is done by the system. The
change in internal energy for the process is
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1) 350 J 2) 450 J 3) -450 J 4) -350 J
34) When is dHsys= dEsys?
1) When qv= qp.
2) In reactions involving only liquids and solids.
3) In reactions running under a vacuum (P=0).
4) All
35) Which of the following reactions could do work of expansion on the surroundings?
1) 2CO(g) + O2(g)
2CO2(g)
2) Fe2O3(s) + 2Al(s)
Al2O3(s) + 2Fe(s)
3) CH4(g) + 2O2(g)
CO2(g) + 2H2O(g)
4) 2N2O(g) 2N2(g) + O2(g)
36) Suppose a gas in a piston is expanded at constant pressure and the temperature goes down. Which
of the following correctly describes the signs for the work, the heat for the system and the energy
change of the system?
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1) Work is positive, q is negative, and dU is negative.
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2) Work is negative, q is may be positive or negative, and dU is negative.
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3) Work is positive, q is may be positive or negative, and dU is negative.
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4) Work is positive, q is positive, and dU is negative.
37) In order to have E 0 for a process, which of the following conditions must be obeyed ?
a) q > 0
b) w > 0
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c) q + w > 0
d) q > 0 such that |q| > |w| (where |q| and |w| are absolute values)
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The correct options are
1) a,b,c & d 2) b &d 3) a & d 4) c & d
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Formula: U H ng RT
Where n g = no. of moles of gaseous products - no. of moles of gaseous reactants
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1) Enthalpy 2) Heat capacity 3) Specific heat 4) Molar heat
-1 -1
9) The molar heat capacity for NaCl is 50.50 J mol K . What is the specific heat?
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1) 0.8640 J g-1 K-1 2) 50.5 J g-1 K-1 3) 8.640 J g-1 K-1 4) 4.184 J g-1 K-1
10) The amount of heat necessary to raise the temperature of 60.0 g of aluminium from 15oC to 55oC is.
(Molar heat capacity of Al is 24 J mol–1K–1)
1) 2.133 J 2) 1.066 J
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Formula: q=n.C m .T
Where n = no. of moles
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Cm = molar heat capacity
T = raise or lowering of temperature
11) The heat capacity of methyl alcohol (MW = 32.05 g/mol) is 80.3 J mol-1 K-1. The quantity of heat
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that will be evolved when the temperature of 2610 g of methyl alcohol falls from 22oC to 2oC
1) 1.5 x 102 kJ 2) 1.3 x 102 kJ 3) 1.7 x 102 kJ 4) 7 kJ
12) The amount of heat absorbed by one mole of an ideal gas in an isochoric process to raise the
temperature from 1.1oC to 11.1oC is 120 kJ/mol. The Cv and Cp values of the gas in kJ mol-1K-1 will
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be
1) 12 kJ & 3.7 kJ 2) 10 kJ & 12 kJ 3) 12 kJ & 20.3 kJ 4) 20.3 kJ & 12 kJ
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Cp
H
T p
qp
T
C p C v nR
13) The difference in Cp and Cv values for liquids and solids will be equal to
1) R 2) nR 3) 2R 4) 0
14) Choose the incorrect statement
1) The molar heat capacities of the metallic elements are almost identical. This is the basis of the Law
of Dulong and Petit, which served as an important tool for estimating the atomic weights of some
elements.
2) The intermolecular hydrogen bonding in water and alcohols results in anomalously high heat
capacities for these liquids; the same is true for ice, compared to other solids.
3) The heat capacity values for graphite and diamond are very high as the solids that are more
“ordered” tend to have larger heat capacities.
4) None.
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Note: The molar heat capacities of metals are almost equal to 3R.
15) The molar heat capacity values of noble gases at contant volume are almost equal to
3R 5R 7R
1) 2) 3) 4) R
2 2 2
Note: In case of noble gases (which are mono-atomic) only three translational degrees of freedom are possible and each of
1 3R 5
these contribute R to heat capacity and hence the Cv = . The Cp value will be given by Cv + R = R
2 2 2
16) The theoretical molar heat capacities of diatomic molecules at constant volume and at fairly high
temperatures is almost equal to
3R 7R 5R
1) 2) R 3) 4)
2 2 2
Note: Diatomic molecules have 3 translational degrees of freedom (contribution of 3R/2), 2 rotational degrees of freedom
7R
(contribution of 1R/2 from each) and 1 vibrational degree of freedom ( contribution of R). Hence Cv = (at high temp.)
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5R
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But at low temperatures (eg., room temperature), the vibrational degree of freedom can be neglected and hence Cv =
2
In the same way, for poly-atomic molecules, the contributions are as follows
1 1 1 3
From three translational degrees of freedom -- R R R R
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1 1 1 3
From three rotational degrees of freedom -- R R R R
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2 2 2 2
From 3N-6 vibrational modes -- (3N-6)R (where N = number of atoms in poly-atomic molecule)
17) Calculate the enthalpy change on freezing of 1.0 mol of water at10.0oC to ice at –10.0oC. Given
fusH = 6.03 kJ mol–1 at 0°C; Cp [H2O(l)] = 75.3 J mol–1 K–1 ; Cp [H2O(s)] = 36.8 J mol–1 K–1
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Note: As the heat supplied is not sufficient to melt the ice completely, finally there will be a mixture of ice and water at 0oC
19) A coffee-cup calorimeter is calibrated by adding 1840 J of heat to the water in the calorimeter and
measuring a 1.72oC rise in temperature. When some NH4Cl(s) is added to the same water in the
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calorimeter, the temperature falls by 1.04oC. The enthalpy change due to the dissolving of NH4Cl(s)
is
1) -1112 J 2) +1250 J 3) +3040 J 4) +1112 J
20) Which of the following statements is true?
1) q = dH at constant P; q = dE at constant T
2) q = dH at constant T; q = dE at constant V
3) q = dH at constant V; q = dE at constant P
4) q = dH at constant P; q = dE at constant V
21) An ice cube at 0oC weighing 9.0 g is dropped into an insulated vessel containing 72 g of water at
50oC. What is the final temperature of water after the ice has melted and a constant temperature has
been reached? The latent heat of fusion of ice is 6.01 kJ/mol and the molar heat capacity of H2O is
75.4 J mol-1K-1.
1) 36oC 2) 40oC 3) 44oC 4) 32oC
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22) What is U o when one mole of liquid water vaporises at 100 C if the heat of vaporisation vap H o
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of water at 100 C is 40.66 kJ.mol ?
1) 40.66 kJ.mol-1 2) 24.66 kJ.mol-1 3) 36.73 kJ.mol-1 4) -40.66 kJ.mol-1
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23) The value of Helium gas is equal to
1) 1.67 cal 2) 1.4 cal 3) 6 cal 4) 10 cal
Cp 5
Note: 1.67 cal
Cv 3
3R
For mono atomic gases Cv 3 cal
2
C p Cv R 5 cal
24) Temperature of one mole of Neon gas is increased by 1oC, hence, increase in internal energy is
1) 5 cal 2) 3 cal 3) 9 cal 4) 2 cal
25) Enthalpy change for a reaction does not depend upon
1) the physical states of reactants and products.
2) use of different reactants for the same product.
3) the nature of intermediate reaction steps.
4) the differences in initial or final temperatures of involved substances.
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26) The specific heat of water is 4.18 J g-1 K-1 and that of stainless steel is 0.51 J g-1 K-1. The heat that
must be supplied to a 750.0 g stainless steel vessel containing 800.0 g of water to raise its tempera-
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ture from 20.0oC to the boiling point of water
1) 6.98 kJ 2) 29.8 kJ 3) 69.8 kJ 4) 298 kJ
27) The temperature of a substance represents
1) the total heat content of a the particles in a substance
2) the speed of the fastest particles in the substance
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3) the speed of the slowest particles in the substance
4) the average kinetic energy of the particles in a system.
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28) A bomb calorimeter was calibrated by burning a sample of benzoic acid (C6H5COOH) which has
a known heat of reaction, H° = –3227 kJ/mol. When 1.22 g of benzoic acid is burned in the
calorimeter, the temperature is increased by 0.75 °C. The heat capacity of the calorimeter and its
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contents will be
1) 32 kJ K-1 2) 4.3 kJ K-1 3) 83 kJ K-1 4) 43 kJ K-1
29) The heat of combustion of methyl alcohol, CH3OH, is -715 kJ mol-1. When 2.85 g of CH3OH
was burned in a bomb calorimeter, the temperature of the calorimeter changed from 24.05 °C to
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THERMOCHEMISTRY
1) Which statement is incorrect about endothermic reactions?
1) the system absorbs energy from its surroundings
2) the enthalpy of products is lower than the enthalpy of the reactants
3) the thermal kinetic energy of the surroundings will decrease
4) the enthalpy change will have a positive value
2) Which of the following is the standard state of carbon at STP?
1) C as CO2 (g) 2) C as graphite (s) 3) C as CH4 (g) 4) C as diamond (s)
3) Which of the following statements is/are true about an exothermic reaction?
I) the energy absorbed in bond breaking is more than the energy released in bond formation
II) the system absorbs energy
III) the potential energy of the reactants is less than the potential energy of the products
IV) the thermal kinetic energy of the surroundings will increase
1) I and III only 2) II and III only 3) II and IV only 4) IV only
4) How much heat is absorbed when 3.00 grams of SiO2 react with excess carbon according to the
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reaction below? r H o for the reaction is +624.7 kJ.
SiO2(s) + 3C(s) SiC(s) + 2CO(g)
1) 208 kJ 2) 5.06 kJ 3) 10.4 kJ 4) 31.2 kJ
5) H of which of the following reactions is equal to the standard enthalpy of formation( f H o ) of
NH3?
1) 2NH3(g)
3H2(g) + N2(g)
2) NH3(g) 3/2H2(g) + 1/2N2(g)
3) 3H(g) + N(g) NH3(g)
4) 3/2H2(g) + 1/2N2(g)
NH3(g)
o
Note: The standard enthalpy of formation, f H , is the amount of heat either liberated or absorbed during the formation
of one mole of a compound from its elements under standard conditions.
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6) Given: H2(g) + Br2(l) 2 HBr(g) ; r H = –72.8 kJ
Calculate the amount of energy absorbed or released when 15.0 g of HBr (g) is formed.
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1) 6.75 kJ released 2) 13.5 kJ released 3) 4.85 kJ absorbed 4) 607 kJ absorbed
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7) Which of the following has non zero standard enthalpy of formation at 25oC?
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1) Cl2(g) 2)O2(g) 3) Na(g) 4) F2(g)
8) The standard heat of formation of NH3 is
(Given N2(g) + 3H2 (g) 2NH (g) ; r H o = -91 kJ )
3
1) +91 kJ 2) + 45.5 kJ 3) -19 kJ 4) -45.5 kJ
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9) The enthalpy change for the reaction of 50 mL of ethylene with 50 mL of H2 at 1.5 atm pressure is
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H = -0.31 kJ. The change in internal energy will be
1) 0.66 kJ.mol-1 2) -0.3024 kJ.mol-1 3) +0.3024 kJ.mol-1 4) -0.66 kJ.mol-1
10) In a constant-volume bomb calorimeter an unknown compound reacted with excess oxygen to give
carbon dioxide and water. The temperature of 2 kg of water in the calorimeter rose from 12.72oC
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to 20.72oC. The heat capacity of the calorimeter is 2.02 kJ.K-1 and the specific heat of water is
4.184 J/goC. The heat given off by the combustion reaction under these conditions is:
1) 41,600 J 2) -41.6 kJ 3) -83.2 kJ 4) -33.5 kJ
Note: The heat given off indicates the internal energy change, as the reaction is occuring at constant volume, and
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perature of 0.5 Kg of water in the calorimeter rose from 12oC to22oC The heat capacity of calorim-
-1
eter is 20.1 kJ.K . The enthalpy of combustion of methane under standard conditions will be
1) 223.1 kJ.mol-1 2) 891.6 kJ.mol-1 3) 888 kJ.mol-1 4) 20.92 kJ.mol-1
Note: Enthalpy of combustion is the amount of heat liberated when one mole of substance is completely burned in excess of
oxygen at standard conditions (constant temperature and pressure). In this case the amount of heat liberated is equal to U .
This value should be converted to H by using the formula. H U n g RT
12) B5H9 burns in air according to the following reaction.
2B5H9(g) + 12O2(g) 5B2O3(s) + 9H2O(l)
What is the molar heat of reaction for the combustion of B5H9 if the reaction between 0.1 g of B5H9
and excess oxygen in a bomb calorimeter raises the temperature of the 852 g of water surrounding
the calorimeter by 1.57oC? [At wts: B = 10.81 amu; H = 1.008 amu; O = 16.00 amu; the heat
capacity of water is 4.184 J / goC]
1) 5.60 x 103 J/mol 2) 9.14 x 102 kJ/mol
3) 3.54 x 103 kJ/mol 4) 4.46 x 103 kJ/mol
13) In the reaction,
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ; r H o = -890.4 kJ
At 1.0 atm and 273 K , how much work is involved per mole of CH4(g) with the volume change that
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occurs upon reaction.
1) -4.5 kJ 2) -2.2 kJ 3) 2.2 kJ 4) 4.54 kJ
Note: The work is done on the system and is equal to 4.54 kJ. Here n g =-ve and hence, H E i.e., -890.4 kJ< - 885.8 kJ.
But if the absolute values are considered, the decrease in internal energy is less than heat liberated. This is because Some
amount of decrease in internal energy, due to loss of heat, is compensated by compression work done on the system.
14) When burned in oxygen, 10.0 g of phosphorus generated enough heat to raise the temperature of
2950 g of water from 8.0oC to 28.0oC. The heat of formation of P4O10 from P4(s) and O2(g) is
1) -30.6 kJ mol-1 2) -306 kJ mol-1 3) -3060 kJ mol-1 4)-6120 kJ mol-1
15) Using the following data:
I) N2(g) + 3O2(g) + H2(g) 2HNO3(aq) ; H = -414.8 kJ
II) N2O5(g) + H2O(g) 2HNO3(aq) ; H = 218.4 kJ
III) 2H2O(g) 2H2(g) + O2(g) ; H = 483.6 kJ
What is the H for the reaction: 2N2O5(g)
2N2(g) + 5O2(g)
1) 90.8 kJ 2) -876.4 kJ 3) 782.8 kJ 4)1750 kJ
16.
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ture of the solution is recorded to be 17.5C. A piece of magnesium ribbon of mass 0.601 g is
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placed in the solution and the final temperature is recorded to be 39.6C. Calculate the molar
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enthalpy change for this reaction : Mg(s) 2 HCl (aq) MgCl2(aq) H2 (g)
1) + 15.4 kJ/mol of Mg 2) - 263 kJ/mol of Mg
3) - 374 kJ/mol of Mg 4) + 5.56 kJ/mol of Mg
23. Which process is not endothermic?
1) H2O(s) H2O(l) 2) 2H2O(g) 2H2(g) + O2(g)
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3) H2O(g) H2O(l) 4) Al2O3 + 2Fe(l) 2Al + Fe2O3
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24. Calculate the H for the following reaction:
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1) 592.2 kJ/mol 2) -197.0 kJ/mol 3) -296.1 kJ/mol 4) -593 kJ/mol
31. Given the following data:
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3/2O2(g) + 2B(s) B2O3(s) Ho = -1264 kJ/mol
O3(g) + 2B(s) B2O3(s) Ho = -1406 kJ/mol
The change in enthalpy for the reaction converting oxygen (O2(g)) to ozone (O3(g)) at 298 K and
1 atm will be i@ R
3/2O2(g) O3(g)
1) -1406 kJ 2) -1264 kJ 3) -2670 kJ 4) +142 kJ
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32. Given the following data
N2(g) + O2(g) 2NO(g) H = 180.8 kJ
1/2N2(g) + O2(g) NO2(g) H = 33.9 kJ
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C6H6(l) + 15/2O2(g)
6CO2(g) + 3H2O(l)
f H o values in kJ/mol are as follows:
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whose heat capacity is 39.0 J/K. The temperature of the resulting solution increased by 3.6 °C.
The standard enthalpy of neutralization of H2SO4(aq) with NaOH(aq) will be
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1) 13.7 kJ mol-1 2) 53.7 kJ mol-1 3) 5.37 kJ mol-1 4) 23.7 kJ mol-1
40) The standard enthalpy of neutralization of acetic acid with sodium hydroxide will be
1) =53.7 kJ mol-1 2) <53.7 kJ mol-1 3) >53.7 kJ mol-1 4) None
Hint: When weak acids or bases participate in the neutralisation, some amount of heat is required for their complete
dissociation. Hence the amount of heat liberated during neutralisation will be less than 53.7 kJ mol-1.
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41) The heat of neutralisation of a strong acid and a strong alkali is 57.0 kJ mol-1. The heat released
when 0.5 mole of HNO3 solution is mixed with 0.2 mole of KOH is
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