Chapter 6: Thermochemistry

∆U = q + w
∆H = ∆U + P∆V
ΔU = ΔH – RT Δn
q=msΔt
q= CΔt
R=0.0821 LXatm/KXmol
1 atmXL = 101.3 J

1. State whether the following reactions are endothermic or exothermic reactions:

a. C (s) + O2 (g)  CO2 (g) ΔH= -393.5 kJ/mol

Exothermic

b. C6H4(OH)2(aq)  C6H4O2(aq) + H2 (g) ΔH= 177 kJ/mol

Endothermic

c. CH4 (g) + 2O2(g)  CO2(g) + 2H2O(l) ΔH= -890.4 kJ/mol

Exothermic

d. 2H2O (l) + 4CO2(g)  5O2(g) + 2C2H2(g) ΔH = 2598.8 kJ/mol

Endothermic

2. A gas expands in volume from 26.7 L to 89.3 L at constant temperature. Calculate the
work done (in joules) if the gas expands a) against a vacuum, b) against a constant
pressure of 1.5 atm, and c) against a constant pressure of 2.8 atm.

a) w= - P ΔV
P = 0 atm in vacuum
w = (-0) (62.6L)
w= 0 atm X L = 0 J
 b) w = (-1.5 atm)(89.3L – 26.7L)
w =(-1.5 atm)(62.6L)
w= - 93.9 atm X L ( 101.3 J/ atmXL) = 9512.07 J
c) w = (-2.8 atm)(89.3L-26.7L)
w = (-2.8 atm)(62.6L)
w= -175.28 atm X L(101.3 J/ atm X L) = 17756 J

3. The work done when a gas is compressed in a cylinder is 462 J. During this process
there is a heat transfer of 128 J from the gas to the surroundings. Calculate the energy
change for this process.

∆U = q + w
w is positive because the surroundings are working on the system, 462J.
q is negative because the system is transferring heat to the surroundings, -128J.
ΔU = (-128J) + (462J)
ΔU = 334J

4. The work done when a gas is compressed in a cylinder is 74 J. During this process
there is a heat transfer of 26 J from the gas to the surroundings. Calculate the internal
energy change for this process.

∆U = q + w
w is positive because the surroundings are working on the system, 73 J.
q is negative because the system is transferring heat to the surroundings, -26J
ΔU = (-26 J) + (73 J)
ΔU = 47 J

5. Calculate the change in internal energy for the formation of 1 mole of CO at 1 atm
and 25OC
C(graphite) + ½ O2 (g)  CO(g) ΔH= -110.5 kJ/mol

ΔU = ΔH – RT Δn
R = 0.0821 LX atm/ mol X K(101.3 J/atm X L) =8.3167 J/ mol X K = 0.0083167 kJ/
mol X K
T= 298 K
Δn = (1 mol CO) – ( 1 mol C + 0.5 mol O2)= - 0.5 mol
ΔU = (-110.5 kJ) – (0.0083167 kJ/ mol X K)(298K)(-0.5 mol)
ΔU = (-110.5 kJ) – (-1.239 kJ) = -109.26 kJ
6. What is the amount of heat evolved in kJ when 1.26 X 104 g of NO2 are produced
according to the following reaction:
2NO(g) + O2 (g)  2NO2 (g) ΔH= -114.6 kJ/mol

Convert g of NO2 to moles of NO2:

1.26 X 104 g of NO2 X ( 1 mol NO2 / 46.01 g NO2) = 273.85 mol NO2
use moles of NO2 with the enthalpy of reaction to solve for heat:
273.85 mol NO2 X ( -114.6 kJ/ 2 mol NO2) = -15691.6 kJ NO2

7. How much heat is evolved in kJ when a) 25 mol of SO2 is converted to SO3 b) when
432 g of O2 is converted to SO3 c) when 125 g of SO3 is produced?
2SO2(g) + O2(g)  2SO3 ΔH= -198.2 kJ/mol

a) use moles of SO2 with the enthalpy of reaction to solve for heat:
25 mol SO2 X ( -198.2 kJ SO2 / 2 mol SO2) = - 2477.5 kJ SO2

b) Convert g of O2 to moles of O2:

432 g O2 S (1 mol O2 / 32 g O2) = 13.5 mol O2
use moles of O2 with the enthalpy of reaction to solve for heat:
13.5 mol O2 X (-198.2 kJ O2/ 1 mol O2) = -2675.7 kJ O2

c) Convert g of SO3 to moles of SO3:

125 g SO3 X ( 1 mol SO3 / 80.07 g SO3) = 1.56 mol SO3
use moles of SO3 witht eh enthalpy of reaction to solve for heat:
1.56 mol SO3 X ( -198.2 kJ SO3 / 2 mol SO3) = -154.7 kJ SO3

8. What is the internal energy of the following reaction if 2 moles of H2O are converted
to H2 and O2 against a pressure of 1.0 atm at 125OC?
2H2O(g)  2H2(g) + O2(g) ΔH= 483.6 kJ/mol

ΔU = ΔH – RT Δn
R = 0.0821 LX atm/ mol X K(101.3 J/atm X L) =8.3167 J/ mol X K = 0.0083167 kJ/
mol X K
T = 398 K
Δn = ( 2 mol H2 + 1 mol O2) – (2 mol H2O) = 1 mol gas
ΔU = (483.6 kJ) – (0.0083167 kJ/ mol X K)(398K)(1 mol)
ΔU = (483.6 kJ) – (3.31 kJ) = 480.29 kJ
9. If I burn 0.315 grams of hexane (C6H14) in a bomb calorimeter containing 5.65 liters
of water, what’s the molar heat of combustion of hexane if the water temperature rises
from 25OC to 80.4OC? The specific heat capacity of water is 4.184 J/g0C.

q=msΔt
qH2O = (5650 g) (4.184 J/gOC)(80.4OC – 25OC)
qH2O = (5650 g) (4.184 J/gOC)(55.4OC)
qH2O = 1309634 J
Because we are looking for the heat of reaction,
qcal = - qrxn
qhexane = -1309634J
q=msΔt
-1309634J = (0.315 g) s (55.4OC)
-1309634J = (17.45 g OC) s
s= -75051 J/ g OC

10. Calculate the ΔHrxn from the ΔH of for the following reactions:
a) PbO (s) + CO (g) -------> Pb (s) + CO2 (g)
ΔH rxn = Σ products – Σ reactants
ΔH rxn = [(Pb(s)+CO2(g))] – [(PbO(s)) + (CO(g))]
ΔH rxn =[ ( 0 kJ) + (-393.5 kJ)] – [(-217.3 kJ) + (-110.5 kJ)]
ΔH rxn = (-393.5 kJ) – (-327.8 kJ)
ΔH rxn = -65.7 kJ

b) SiH4 (g) + 2 O2 (g) -------> SiO2 (s) + 2 H2O (l)

ΔH rxn = Σ products – Σ reactants
ΔH rxn = [ (SiO2 (s)) + 2 X (H2O(l)] – [ SiH4(g) + 2 X O2(g)
ΔH rxn = [ (-910.9kJ) + 2X(-285.8kJ)] – [ (34.3) + 2 X (0)]
ΔH rxn = (-1482.5 kJ) – (34.3 kJ)
ΔH rxn = -1516.8 kJ

c) 2 FeS2 (s) + 5 1/2 O2 (g) -------> Fe2O3 (s) + 4 SO2 (g)

ΔH rxn = Σ products – Σ reactants
ΔH rxn = [ (Fe2O3(s)) + 4 X (SO2(g))] – [ 2X FeS2 (s) + 5.5 O2(g)]
ΔH rxn = [ (-824.2 kJ) + 4 X (-296.8 kJ)] – [ 2X-177.5 kJ+ 5.5 X O]
ΔH rxn = (-2011.4 kJ) – ( -355kJ)
ΔH rxn = -1656.4 kJ
 ΔHof kJ/mol ΔHof kJ/mol

CO (g) -110.5 Pb (s) 0

CO2 (g) -393.5 PbO (s) -217.3

Fe2O3 (s) -824.2 SiH4 (g) 34.3

FeS2 (s) -177.5 SiO2 (s) -910.9

H2O (l) -285.8 SO2 (g) -296.8

O2 (g) 0

11. Determine the ΔHrxn for the following:

Mn (s) + O2 (g)  MnO2 (s)

Given:

A. 4 Al (s) + 3 O2 (g)  2 Al2O3 (s) ΔHrxn = -3352 kJ/mol

B. 4 Al (s) + 3 MnO2 (s)  3 Mn (s) + 2 Al2O3 (s) ΔHrxn = -1937 kJ/mol

A. ΔHrxn = -3352 kJ/mol ÷ 3 = -1117.33 kJ

4/3 Al(s) + 1 O2 (g)  2/3 Al2O3 (s)

B. ΔHrxn = 1937 kJ/mol ÷ 3 = 645.67 kJ

1 Mn(s) + 2/3 Al2O3 (s)  4/3 Al(s) + 1 MnO2 (s)

Δ Hrxn = (-1117.33 kJ ) + (645.67 kJ) = -471.66 kJ

O2(g) + Mn(s)  MnO2(s)

12. Determine the ΔHrxn for

C3H4 (g) + 2 H2 (g)  C3H8 (g)

Given:

A. 2 H2 (g) + O2 (g)  2 H2O (l) ΔHrxn = -571.6 kJ/mol

B. C3H4 (g) + 4 O2 (g)  3 CO2 (g) + 2 H2O (l) ΔHrxn = -1937 kJ/mol

C. C3H8 (g) + 5 O2 (g) 3 CO2 (g) + 4 H2O (l) ΔHrxn = -2220 kJ/mol

A. ΔHrxn = -571.6 kJ/mol

2 H2 (g) + O2 (g)  2 H2O (l)

B. ΔHrxn = -1937 kJ/mol

C3H4 (g) + 4 O2 (g)  3 CO2 (g) + 2 H2O (l)

C. ΔHrxn = 2220 kJ/mol

3 CO2 (g) + 4 H2O (l)  C3H8 (g) + 5 O2 (g)

ΔHrxn = (-571.6 kJ) + (-1937 kJ) + (2220 kJ) = -288.6 kJ

2 H2 (g) + C3H4 (g)  C3H8 (g)

13. Calculate ∆H for the reaction

C2H4(g) + H2(g)→C2H6(g),
Given:

A. C2H4(g) + 3 O2(g)→2 CO2(g) + 2 H2O (l) ∆H = -1411 kJ

B. C2H6(g) + 7/2 O2(g)→2 CO2(g) + 3H2O (l) ∆H = -1560 kJ

C. H2(g) + 1/2 O2(g) →H2O (l) ∆H = -285.8 kJ

A. ∆H = -1411 kJ

C2H4(g) + 3 O2(g)→2 CO2(g) + 2 H2O (l)

B. ∆H = 1560 kJ

2 CO2(g) + 3H2O (l)  C2H6(g) + 7/2 O2(g)

C. ∆H = -285.8 kJ

H2(g) + 1/2 O2(g) →H2O (l)

ΔHrxn = (-1411 kJ) +(1560 kJ) +(-285.8 kJ) = -136.8 kJ

C2H4(g) + H2(g)  C2H6(g)

14. Calculate ∆Η for the reaction

2 Al (s) + 3 Cl2(g) →2 AlCl3(s)
Given:

A. 2 Al (s) + 6 HCl (aq) →2 AlCl3(aq) + 3 H2(g) ∆H = -1049 kJ

B. HCl (g) →HCl (aq) ∆H = -74.8 kJ

C. H2(g) + Cl2(g) →2 HCl (g) ∆H = -1845 kJ

D. AlCl3(s) →AlCl3(aq) ∆H = -323 kJ

A. ∆H = -1049 kJ

2 Al (s) + 6 HCl (aq) →2 AlCl3(aq) + 3 H2(g)

B. ∆H = -74.8 kJ X 6 = -448.8 kJ

6 HCl (g) →6 HCl (aq)

C. ∆H = -1845 kJ X 3 = -5535 kJ

3 H2(g) + 3 Cl2(g) →6 HCl (g)

D. ∆H = 323 kJ X 2= 646 kJ

2 AlCl3(aq)  2 AlCl3(s)

ΔHrxn = (-1049 kJ) + (-448.8 kJ) +(-5535 kJ) +(646 kJ) = -6386.8 kJ

2 Al (s) +3 Cl2(g) 2 AlCl3(s)