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NOTE: PART 2 CONTAINS QUESTIONS FROM ENTROPY AND FREE ENERGY
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CHEMICAL THERMODYNAMICS (PART-I)
IIT-JEE & AIEEE
GATE, JAM & CSIR EXAMS
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a) Thermodynamics will help in predicting whether a physical or chemical change is possible under
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given conditions.
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b) Thermodynamics only deals with the initial and final states of the system and is not helpful in
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evolving the mechanism of the process.
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c) The rate of a reaction can be evolved from thermodynamics.
d) The mechanism of a reaction can be evolved from thermodynamics.
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1) a only 2) a & b 3) a,b & c 4) a & d
2) Choose the incorrect statement
2) Closed systems can only exchange energy and do not exchange matter with its surroundings.
3) Isolated systems can exchange energy and matter with its surroundings.
4) None.
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capacity; are
1) a, b & c 2) b & e 3) c & e 4) None
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17) Which of the following is true about isothermal free expansion of a gas?
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1) dU = 0 2) dT = 0 3) PextdV = 0 4) All
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18) The work done during isothermal irreversible change will be given by
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Vf Vf
1) -Pext(Vf-Vi) 2) 2.303nRT log
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Vi Vi
Note: In the irreversible process, the work is done against constant external pressure which differs largely from the internal
19) The work done during an isothermal reversible change will be given by
Vf Vf
1) -Pext(Vf-Vi) 2) 2.303nRT log 3) nRT log 4) zero
Vi Vi
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Note: In case of reversible process, the internal pressure is almost equal to the external pressure. This internal pressure is
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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
p :/ D
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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
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?
1) +q, +w, +E 2) -q, -w, -E 3) -q, -w, +E 4) -q, +w, -E
30) 11.2 L of a hydrogen gas at 273 K temperature and 1 atm of pressure in a sealed rigid container is
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
qv dU =
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
Thermodynamics Part-I: Prepared by V. Aditya vardhan adichemadi(at)gmail.com 4
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
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
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35) Which of the following reactions could do work of expansion on the surroundings?
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1) 2CO(g) + O2(g)
2CO2(g)
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2) Fe2O3(s) + 2Al(s)
Al2O3(s) + 2Fe(s)
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3) CH4(g) + 2O2(g)
CO2(g) + 2H2O(g)
4) 2N2O(g) 2N2(g) + O2(g)
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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
37) In order to have E 0 for a process, which of the following conditions must be obeyed ?
a) q > 0
b) w > 0
c) q + w > 0
p :/ D
d) q > 0 such that |q| > |w| (where |q| and |w| are absolute values)
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pressure.
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1) -2 kJ 2) -0.27 kJ 3) +2 kJ 4) +0.53 kJ
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Note: Now +2 kJ > 0.27 kJ. Therefore dU > dH. This is true even when the absolute values are taken. Why? In this case the
value of work done on the system during compression is greater than the amount of heat lost.
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6) If water vapour is assumed to be a perfect gas, molar enthalpy change for vapourisation of 1 mol of
water at 1bar and 100°C is 41kJ mol-1. The internal energy change, when 1 mol of water is vaporised
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at 1 bar pressure and 100°C will be
1) 37.9 kJ mol–1 2) 41 kJ mol–1 3) 47.9 kJ mol–1 4) 18.3 kJ mol–1
Reaction: H2(liquid)
H2(gas)
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) 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.
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11) The heat capacity of methyl alcohol (MW = 32.05 g/mol) is 80.3 J mol-1 K-1. The quantity of heat
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
be
1) 12 kJ & 3.7 kJ 2) 10 kJ & 12 kJ 3) 12 kJ & 20.3 kJ 4) 20.3 kJ & 12 kJ
Thermodynamics Part-I: Prepared by V. Aditya vardhan adichemadi(at)gmail.com 6
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.
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2) The intermolecular hydrogen bonding in water and alcohols results in anomalously high heat
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capacities for these liquids; the same is true for ice, compared to other solids.
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3) The heat capacity values for graphite and diamond are very high as the solids that are more
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“ordered” tend to have larger heat capacities.
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4) None.
Note: The molar heat capacities of metals are almost equal to 3R.
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15) The molar heat capacity values of noble gases at contant volume are almost equal to
3R 5R 7R
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
R
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these contribute R to heat capacity and hence the Cv = . The Cp value will be given by Cv + R =
2 2 2
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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)
p :/ D
2 2 2
Note: Diatomic molecules have 3 translational degrees of freedom (contribution of 3R/2), 2 rotational degrees of freedom
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7R
(contribution of 1R/2 from each) and 1 vibrational degree of freedom ( contribution of R). Hence Cv = (at high temp.)
2
5R
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
2 2 2 2
1 1 1 3
From three rotational degrees of freedom -- R R R R
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
1) 7.151 kJ 2) -6.03 kJ 3) 3.63 kJ 4) -7.151 kJ
18) If 1000 calories are added to 20 g of ice at -10oC, the final temperature will be
(Specific heat of ice = 0.48 cal/g-K and Heat of fusion of ice = 80 cal/g.)
1) 380 K 2) 0 K 3) 273 K 4) 283.2 K
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
Thermodynamics Part-I: Prepared by V. Aditya vardhan adichemadi(at)gmail.com 7
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
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.
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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 ?
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1) 40.66 kJ.mol-1 2) 24.66 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
2
C p Cv R 5 cal
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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
p :/ D
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?
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I) the energy absorbed in bond breaking is more than the energy released in bond formation
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II) the system absorbs energy
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III) the potential energy of the reactants is less than the potential energy of the products
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IV) the thermal kinetic energy of the surroundings will increase
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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) 2NH3(g)
3H2(g) + N2(g)
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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)
p :/ D
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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.
1) 6.75 kJ released 2) 13.5 kJ released 3) 4.85 kJ absorbed 4) 607 kJ absorbed
7) Which of the following has non zero standard enthalpy of formation at 25oC?
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
9) The enthalpy change for the reaction of 50 mL of ethylene with 50 mL of H2 at 1.5 atm pressure is
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
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
Thermodynamics Part-I: Prepared by V. Aditya vardhan adichemadi(at)gmail.com 9
not is not equal to the enthalpy change.
11) In a constant - volume bomb calorimeter, 4g of methane is burned in excess of oxygen. The tem-
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]
m
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1) 5.60 x 103 J/mol 2) 9.14 x 102 kJ/mol
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3) 3.54 x 103 kJ/mol 4) 4.46 x 103 kJ/mol
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13) In the reaction,
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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
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2950 g of water from 8.0oC to 28.0oC. The heat of formation of P4O10 from P4(s) and O2(g) is
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16.
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19. Given the following thermochemical equation
2 C2H3Br (g) + 5 O2 (g) 4 CO2 (g) + 2 H2O (g) + 2 HBr (g) Hº = 1150 kJ
What is the change in energy accompanying the production of 1.5 moles of CO2(g)?
1) 1725 kJ 2) 766.7 kJ 3) 431.3 kJ 4) 9.799 kJ
20. When 1.75 g of CaCl2 dissolves in 125 g of water in a coffee-cup calorimeter, the temperature
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increases by 2.44ºC. What is the heat change per mole of CaCl2 dissolved? Assume that all the
heat is absorbed by the water.
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temperature change of the water is measured to be +2.10C. The specific heat capacity of water
is 4.184 J/gC. What is the thermochemical equation for this process?
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f H o (H2O(l)) = -285.8 kJ/mole]
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1) +699.7 kJ 2) -658.6 kJ 3) -1926.3 kJ 4) -2018 kJ
28. Using the following data:
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N2(g) + 3O2(g) + H2(g) 2HNO3(aq)
ich RD H = -414.8 kJ
N2O5(g) + H2O(g) 2HNO3(aq) H = 218.4 kJ
2H2O(g) 2H2(g) + O2(g) H = 483.6 kJ
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30. Calculate the H for the reaction:
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33. Calculate the enthalpy change, Ho, for the combustion of benzene, C6H6, given the following
C6H6(l) + 15/2O2(g)
6CO2(g) + 3H2O(l)
f H o values in kJ/mol are as follows:
C6H6(l) = 49.0; CO2(g) = -393.5; H2O(l) = -285.8
1) -3169.4 kJ 2) 3267.4 kJ 3) -728.3 kJ 4) -3267.4 kJ
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34. Calculate H for the reaction: Na2O(s) + SO3 (g) Na2SO4(s) given the following:
(1) Na(s) + H2O(l)
NaOH(s) + 1/2 H2(g) Ho = – 146 kJ
(2) Na2SO4 (s) + H2O(l) 2NaOH(s) + SO3(g) Ho = + 418 kJ
(3) 2Na2O (s) + 2H2(g) 4Na(s) + 2H2O(l) Ho = + 259 kJ
1) + 823 kJ 2) – 581 kJ 3) – 435 kJ 4) + 531 kJ
35. Given equations (1) and (2), calculate the enthalpy change for equation (3).
m
Ho = -775 kJ
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(1) Pb(s) + PbO2(s) + 2 SO3(g) 2 PbSO4(s)
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(2) SO3(g) + H2O(l) H2SO4(aq) Ho = -133 kJ
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(3) Pb(s) PbO2(s) 2 H2SO4(aq) 2 PbSO4(s) 2 H2O(l)
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1) – 908 kJ 2) – 642 kJ 3) – 509 kJ 4) + 642 kJ
36. Given that : S(s) + O2(g) SO2(g) Hº = – 296.8 kJ/mol
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2 SO3(g) 2 SO2(g) + O2(g) Hº = + 197.8 kJ/mol
Determine the enthalpy change of the reaction: 2 S(s) + 3 O2(g) 2 SO3(g)
38. Given equations (I), (II), and (III), calculate the standard enthalpy of formation of acetylene,
C2H2, as shown in equation (IV).
(I) C (s) + O2 (g) CO2 (g) Hº = – 393.5 kJ
(II) H2 (g) + ½ O2 (g) H2O (l) Hº = – 285.8 kJ
p :/ D
(III) 2 C2H2 (g) + 5 O2 (g) 4 CO2 (g) + 2 H2O (l) Hº = – 2598.8 kJ
htt V. A