THERMOCHEMISTRY EXERCISES

1. Calculate the enthalpy of formation of methane (CH4) from the elements, knowing that the
enthalpy of combustion of methane is -212,79 kcal/mol and that the enthalpies of formation of CO 2
and H2O are respectively -93,69 kcal/mol and -68,3 kcal/mol.
Write the reaction corresponding to each data given in the text:
Hc (CH4) = -212.79 kcal/mol CH4 + 2O2 CO2 + 2H2O (1)
Hf (CO2) = -93.69 kcal/mol C + O2 CO2 (2)
Hf (H2O) = -68.3 kcal/mol H2 + 1/2O2 H2O (3)
In order to obtain the reaction of formation of CH4 we have to do: (2) + 2*(3) (1)
C + O2 + 2H2 + O2 + CO2 + 2H2O CO2 + 2H2O + CH4 + 2O2 after simplification:
C + 2H2 CH4
So : Hf (CH4) = Hf (CO2) + 2*Hf (H2O) - Hc (CH4)
Hf (CH4) = -93.69 + 2*(-68.3) (-212.79) = -17.50 kcal/mol
2. The enthalpies of combustion of formaldehyde, CH 2O, and of methanol, CH3OH, are
respectively: - 136,42 kcal/mol and - 173,64 kcal/mol. Calculate the enthalpy of formation for the
reaction: CH2O + H2 CH3OH Knowing the enthalpy of combustion of hydrogen is - 68,3 kcal/mol.
Write the reaction corresponding to each data given in the text:
Hc (CH2O) = - 136,42 kcal/mol CH2O + O2 CO2 + H2O (1)
Hc (CH3OH) = - 173,64 kcal/mol CH3OH + 3/2O2 CO2 + 2 H2O (2)
Hc (H2) = -68.3 kcal/mol H2 + 1/2O2 H2O (3)
In order to obtain the reaction CH2O + H2 CH3OH we have to do: (1) + (3) (2)
CH2O + O2 + H2 + 1/2O2 + CO2 + 2 H2O CO2 + H2O + H2O + CH3OH + 3/2O2 after simplification:
CH2O + H2 CH3OH
So : Hf (CH3OH) = Hc (CH2O) + Hc (H2) - Hc (CH3OH)
Hf (CH3OH) = - 136,42 + (-68.3) (- 173,64) = -31.08 kcal/mol
3. Calculate the enthalpy of formation of ethanol, CH3CH2OH, knowing that the enthalpy of
combustion is -326,68 kcal/mol and that the enthalpy of combustion of C and of H 2 are
respectively -93,69 kcal/mol and -68,3 kcal/mol.
Write the reaction corresponding to each data given in the text
Hc (CH3CH2OH) = -326,68 kcal/mol CH3CH2OH + 3O2 2CO2 + 3H2O (1)
Hc (C) = -93,69 kcal/mol C + O2 CO2 (2)
Hc (H2) = -68.3 kcal/mol H2 + 1/2O2 H2O (3)
In order to obtain the reaction we have to do: 2*(2) + 3*(3) (1)
2C + 2O2 + 3H2 + 3/2O2 + 2CO2 + 3H2O 2CO2 + 3H2O + CH3CH2OH + 3O2 after simiplification:
2C + 3H2 + 1/2O2 CH3CH2OH
So : Hf (CH3CH2OH) = 2*Hc (C) + 3*Hc (H2) - Hc (CH3CH2OH)
Hf (CH3CH2OH) = 2*(-93,69) + 3*(-68.3) (-326,68) = -65.6 kcal/mol
4. Calculate the heat of reaction obtained by burning 1 kg of carbon containing 78% of C, 8,1% of
H2 ; the difference from 100 is humidity, ashes, oxygen, sulfur, nitrogen, knowing that the heat of
combustion of C and H2 are respectively -93,69 kcal/mol and -68,3 kcal/mol.
At p = cost, H = Q
Here Q = QC + Q H2 = nC*Hc (C) + nH2*Hc (H2)
Burning 1kg of carbon we obtain pesC = 780g e pesH2 = 81g, calculate the corresponding number of
moles:
nC = pesC/PM = 780/12 = 65 mol
nH2 = pesH2/PM = 81/2 = 40.5 mol
So Q = 65*(-93.69) + 40.5*(-68.3) = -8856 kcal

5. 500 l of a mixture in standard conditions formed by (volume %) 35% of ethane, C 2H6, 25% of
butane, C4H10 and 40% of H2 is burnt. Calculate the heat formed during the combustion.
For ethane: HC = -372,81 kcal/mol
For butane: HC = -683,4 kcal/mol
For hydrogen: HC = -68,3 kcal/mol
So in 500 l we have
35% di C2H6 or VC2H6 = 0.35*500 = 175 l
25% di C4H10 or VC4H10 = 0.25*500 = 125 l
40% di H2 or VH2 = 0.40*500 = 200 l
Standard conditions mean p = 1atm and T = 273K
So we can calculate the moles of each compound via the law of perfect gases:
nC2H6 = (p* VC2H6)/RT = (1*175)/(0.08206*273) = 7.81mol
nC4H10 = (p* VC4H10)/RT = (1*125)/(0.08206*273) = 5.58mol
nH2 = (p* VH2)/RT = (1*200)/(0.08206*273) = 8.92mol
Q = nC2H6 * HC(C2H6) + nC4H10 * HC(C4H10) + nH2 * HC(H2)
Q = 7.81*(-372.81) + 5.58*(-683.4) + 8.92*(-68.3) = -7334.25 kcal
6. The air withdrawn from a mine contains methane; after the reaction of combustion was initiated,
from 10 l of air, (in standard conditions) the heat of combustion obtained is -1635 cal. Calculate the
volume percentage of methane in air.
HC(methane) = - 212,790 kcal/mol
Q = nCH4* HC(CH4)
So nCH4 = Q/ HC(CH4)
nCH4 = -1.635/(-212.790) = 7.69.10-3 mol
Calculate the corresponding volume of methane through the law of perfetc gases, knowing that we
are in standard conditions (p = 1 atm and T = 273K).
VCH4 = nCH4*R*T/p
VCH4 = 7.69.10-3*0.08206*273/1 = 0.172 l
So %vCH4 = (VCH4/Varia)*100
%vCH4 = (0.172/10)*100 = 1.72%
7. Calculate the heat formed when 4,20 l of H2 react with an excess of di N2 at p = 200 atm T = 523
K to form ammonia, knowing that Hf (NH3) = - 46,19 kJ/mol.
The reaction of formation of NH3 is 1/2N2 + 3/2H2 NH3
1/2x
3/2x
x
Calculate the moles of H2 via the law of perfect gases from the data of the text:
nH2 = pVH2/RT
nH2 = (200*4.20)/(0.08206*523) = 19.57 mol = 3/2x so x = 13.047
nNH3 = x = 13.047 mol
Q = nNH3* Hf (NH3)
Q = 13.047*(- 46,19) = -602.6 kJ
8. Calculate the H of formation of CO from the elements knowing that, for CO 2(g), Hform = 393,5
kJ/mol and for the oxidation of CO(g) to CO2(g), H = - 283,9 kJ/mol.
Write the reaction corresponding to each data given in the text:
Hf (CO2) = -393.5 kJ/mol C + O2 CO2 (1)
Hox (CO) = - 283,9 kJ/mol CO + 1/2O2 CO2 (2)
In order to obtain the reaction of formation of CO we have to do: (1) - (2)
C + O2 + CO2 CO2 + CO + 1/2O2 after simiplification:
C + 1/2O2 CO2

So : Hf (CO) = Hf (CO2) -Hox (CO)

Hf (CO) = -393.5 - (-283.9) = -109.6 kJ/mol
9. Calculate H for the decomposition of CaCO3(s) to CaO(s) and CO2(g) knowing that:
Hform of CO2(g) = - 393,5 kJ/mol
Hform of CaO(s) = - 635,5 kJ/mol
Hform of CaCO3(s) = - 1206,9 kJ/mol
Write the reaction corresponding to each data given in the text:
Hform (CO2) = -393.5 kJ/mol C + O2 CO2 (1)
Hform di CaO(s) = - 635,5 kJ/mol Ca + 1/2O2 CaO (2)
Hform di CaCO3(s) = - 1206,9 kJ/mol Ca + C + 3/2O2 CaCO3 (3)
In order to obtain the reaction of decomposition of CaCO 3(s) to CaO(s) and CO2(g) we have to do:
(1) + (2) (3)
C + O2 + Ca + 1/2O2 + CaCO3 CO2 + CaO + Ca + C + 3/2O2
After simiplification:
CaCO3 CO2 + CaO
So : Hdec (CaCO3) = Hform(CO2) + Hform(CaO) - Hform(CaCO3)
Hdec (CaCO3) = -393.5 + (-635.5) (-1206.9) = -177.9 kJ/mol
10. Calculate H for the reaction:
Na(s) H2O Na hydr e

Knowing that:
Hsubl. Na = 104,6 kJ/mol
Hion.Na(g) = 493,7 kJ/mol
Hhydr Na+ = - 397,5 kJ/mol
Write the reaction corresponding to each data given in the text:
Hsubl. Na = 104,6 kJ/mol Na(s) Na(g) (1)
Hion.Na(g) = 493,7 kJ/mol Na(g) Na+(g) + e- (2)
Hidr Na+ = - 397,5 kJ/mol Na+(g) H2 O Na+idr (3)
In order to obtain the reaction Na(s) H 2O Na idr e we have to do: (1) + (2) + (3)
Na(s) + Na(g) + Na+(g) H2 O Na(g) + Na+(g) + e- + Na+idr
After simplification:
Na(s) H2 O Na+idr + eSo : H = Hsubl. Na + Hion.Na(g) + Hidr Na+
H = 104,6 + 493,7 + (-397,5) = -200.8 kJ/mol
11. Calculate the Hform of glucose,C6H12O6 knowing that for:
CO2(g) Hform = - 393,5 kJ/mol
H2O(l) Hform = - 285,8 kJ/mol
C6H12O6(s) Hcomb = - 2815,8 kJ/mol
Write the reaction corresponding to each data given in the text:
Hform(CO2) = - 393,5 kJ/mol C + O2 CO2 (1)
Hform(H2O) = - 285,8 kJ/mol H2 + 1/2O2 H2O (2)
Hcomb(C6H12O6) = - 2815,8 kJ/mol C6H12O6 + 6O2 6CO2 + 6H2O (3)
In order to obtain the reaction of formation of glucose we have to do: 6*(1) + 6*(2) - (3)
6C + 6O2 + 6H2 + 3O2 +6CO2 + 6H2O 6CO2 + 6H2O + C6H12O6 + 6O2
After simplification:
6C + 6H2 + 3O2 C6H12O6
So : Hform(C6H12O6) = 6*Hform(CO2) + 6*Hform(H2O) - Hcomb(C6H12O6)
Hform(C6H12O6) = 6*(-393.5) + 6*(-285.8) (-2815.8) = -1260 kJ/mol

12. Calculate Hcomb of CH4 knowing that:

Hform CO2(g) = - 393,5 kJ/mol; Hform H2O(l) = - 285,8 kJ/mol; Hform CH4 = - 74,85 kJ/mol
Write the reaction corresponding to each data given in the text:
Hform(CO2) = - 393,5 kJ/mol C + O2 CO2 (1)
Hform(H2O) = - 285,8 kJ/mol H2 + 1/2O2 H2O (2)
Hform(CH4) = - 74,85 kJ/mol C + 2H2 CH4 (3)
In order to obtain the reaction of combustion of CH4 we have to do: (1) + 2*(2) - (3)
C + O2 + 2H2 + O2 + CH4 CO2 + 2H2O + C + 2H2
After simplification:
CH4 + 2O2 CO2 + 2H2O
So : Hcomb (CH4) = Hform(CO2) + 2*Hform(H2O) - Hform(CH4)
Hcomb (CH4) = - 393,5 + 2*(-285.8) (-74,85) = -890.25 kJ/mol
13. Calculate the heat produced at p = 1 atm and T = 25C during the combustion of 1,2 m 3 of a
mixture formed by, in volume, 70% of CH4 and 30% of H2, to liquid H2O, knowing the the enthalpies
of combustion of CH4 and H2 are respectively -212,7 kcal/mol and -68,4 kcal/mol.
Q = nCH4*Hcomb(CH4) + nH2*Hcomb(H2)
We have the total pressure and the temperature, so via the law of perfect gases, we can calculate
the total number of mole:
nTOT = pV/RT e V = 1,2 m3 = 1200 dm3 = 1200 l
nTOT = (1*1200)/(0.08206*298) = 49.07 mol
We know that %vi = Xi*100
So %vCH4 = (nCH4/nTOT)*100
nCH4 = 0.70*nTOT
nCH4 = 0.70*49.07 = 34.349 mol
%vH2 = (nH2/nTOT)*100
nH2 = 0.30*nTOT
nH2 = 0.30*49.07 = 14.721 mol
Q = 34.349*(-212.7) + 14.721*(-68.4) = -8313 kcal
14. Consider 1 m3 of a mixture in standard conditions (p = 1 atm, T = 25C) formed by, in volume,
10% of N2, 30% of H2, 60% of CO. Knowing the standard enthalpies of the following reactions:
2CO(g) + O2 2 CO2(g)
H = - 135 kcal
2H2(g) + O2 (g) 2H2O(l)
H = - 136,6 kcal
Calculate the enthalpy of reaction for the combustion of this mixture.
At p = cost, we know that H = Q, moreover N 2 is inert, therefore it doesnt take part in the reaction,
so H = Q = nH2* H(H2) + nCO*H(CO)
We can see that the reactions given and the corresponding enthalpies are not molar, all are
doubled, so:
H(CO) = -135/2 = -67.5 kcal/mol
H(H2) = -136.6/2 = -68.3 kcal/mol
Lets calculate the moles of CO and H2:
But first we calculate the total number of mole via the law of perfect gases:
nTOT = pV/RT e V = 1 m3 = 1000 dm3 = 1000 l
nTOT = (1*1000)/(0.08206*298) = 40.89 mol
We know that %vi = Xi*100
So %vCO = (nCO/nTOT)*100
nCO = 0.60*nTOT
nCO = 0.60*40.89 = 24.534 mol
%vH2 = (nH2/nTOT)*100
nH2 = 0.30*nTOT
nH2 = 0.30*40.89 = 12.267 mol

H = 24.534*(-67.5) + 12.267*(-68.3) = -2494 kcal

15. The combustion of 1 mole of glucose, C 6H12O6 at p = cost of 1 atm and T = 20C, produces
-673 kcal. Calculate E for this process.
E = H pV
But we know, from the law of perfect gases that pV = nRT
The reaction of combustion of glucose is C 6H12O6 + 6O2(g) 6CO2(g) + 6H2O So 6 moles of
oxygen (gas) give 6 moles of CO2 (gas): n = 6 6 = 0
So nRT = pV = 0
and E = H = -673 kcal
16. Calculate E for the total combustion of 1 mole of stearic acid, C 18H36O2 , at p = 1 atm, T =
293,2 K, knowing that H = - 2711,8 kcal.
E = H pV
But we know, from the law of perfect gases that pV = nRT
The reaction of combustion of glucose is C18H36O2 + 26O2(g) 18CO2(g) + 18H2O so 26 moles of
oxygen (gas) give 18 moles of CO2 (gas): n = 18 26 = -8
So nRT = -8*1.987*293.2 = -4661 cal CARREFUL, YOU MUST USE THE VALUE OF R TAKING
INTO ACCOUNT THE CALORIES R = 1.987 cal/(mol.K)
So pV = -4.661 kcal
and E = -2711.8 (-4.661) = -2707.1 kcal
17. Knowing that, for the combustion of 1 mole of glucose, C 6H12O6, E = - 673 kcal and for the
combustion of 1 mole of di stearic acid, C 18H36O2, E = - 2707,1 kcal, calculate H for both the
combustions of glucose and stearic acid, at T = 293,2 K and p = 1 atm.
E = H pV
But we know, from the law of perfect gases that pV = nRT
The reaction of combustion of glucose is C 6H12O6 + 6O2(g) 6CO2(g) + 6H2O So 6 moles of
oxygen (gas) give 6 moles of CO2 (gas): n = 6 6 = 0
So nRT = pV = 0
and E = H = -673 kcal
H = E + pV
But we know, from the law of perfect gases that pV = nRT
The reaction of combustion of glucose is C18H36O2 + 26O2(g) 18CO2(g) + 18H2O so 26 moles of
oxygen (gas) give 18 moles of CO2 (gas): n = 18 26 = -8
So nRT = -8*1.987*293.2 = -4661 cal
So pV = -4.661 kcal
and H = -2707.1 + (-4.661) = -2712.4 kcal
18. Calculate H, S and G at 25C for the reaction:
2CH3OH(g) + 3O2(g) 2CO2(g) + 4H2O(g)
Knowing that: Hf (CH3OH) = -200.7 kJ/mol; Sf(CH3OH) = 239.8 J/(mol.K);
Hf (O2) = 0.0 kJ/mol; Sf(O2) = 205.1 J/(mol.K);
Hf (CO2) = -393.5 kJ/mol; Sf(CO2) = 213.7 J/(mol.K);
Hf (H2O) = -241.8 kJ/mol; Sf(H2O) = 188.8 J/(mol.K);
Write the reaction corresponding to each data given in the text:
C + 2H2 + 1/2 O2 CH3OH (1)
O2 (2)
C + O2 CO2 (3)

H2 + 1/2O2 H2O (4)

In order to obtain the reaction: 2CH 3OH(g) + 3O2(g) 2CO2(g) + 4H2O(g) we have to do: 2*(3) +
4*(4) (2*(1)+ 3*(2))
So H = 2*Hf (CO2) + 4*Hf (H2O) (2*Hf (CH3OH) + 3*Hf (O2))
H = 2*(-393.5) + 4*(-241.8) (2*(-200.7) + 3*0) = -1353 kJ/mol
and S = 2*Sf (CO2) + 4*Sf (H2O) (2*Sf (CH3OH) + 3*Sf (O2))
S = 2*213.7 + 4*188.8 (2*239.8 + 3*205.1) = 87.7 J/(mol.K)
In the end G = H - T S
G = -1353 (273+25)*87.7.10-3 = -1379 kJ