Question 1

(a) Define the standard enthalpy of (i) combustion,ΔHθc, and (ii) formation, ΔHθf

(b) Given the following standard enthalpies of combustion, ΔHθc (298K, 1 atm)

C(s) -393 kJmol-1; H2(g) -285.6 kJmol-1; C2H6(g) -1560 kJmol-1

Note: the first two enthalpies correspond to the standard enthalpy of formation of carbon dioxide and
water respectively

Calculate the standard enthalpy of formation of ethane, ΔHθf(C2H6(g))

(c) Given the following bond enthalpies (bond energies) in kJmol -1

bond ΔHBE: C-H 412; C-C 347; O-H 464; O=O 498; C=O 805 (for CO 2 only); C-O 358

Note in other questions the C=O bond enthalpy is 743 kJmol-1 or a similar value in organic
molecules such as aldehydes, ketones, esters, carboxylic acids etc. BUT NOT in CO 2 (eg see
Question 4)

(i) Calculate the enthalpy of combustion of ethane assuming all the species are gaseous.

(ii) Why in (i) do you not get the value of -1560 kJ mol -1?

ANSWERS to the ΔH enthalpy Q's  *  Thermochemistry and Enthalpy Notes

 
Question 2

Given the following standard enthalpies of combustion ΔHθc (298K, 1 atm)

C(s) -393 kJmol-1; H2(g) -285.6 kJmol-1; C8H18(l) -5512 kJmol-1

Calculate the standard enthalpy of formation of octane, ΔHθf(C8H18(l))

ANSWERS to the ΔH enthalpy Q's  *  Thermochemistry and Enthalpy Notes

 
Question 3

(a) Given the following standard enthalpies of combustion ΔHθc(298K, 1 atm)

C(s) -393 kJmol-1; H2(g) -285.6kJ mol-1

and the standard enthalpy of formation of liquid cyclohexane, ΔH θf(C6H12(l)) = -156 kJ mol-1

Calculate the standard enthalpy of combustion of cyclohexane, ΔH θc(C6H12(l))

(b) Using the appropriate bond energies from Q1c, calculate the theoretical enthalpy of
combustion of cyclohexane, assuming ALL reactants and products are gases.
Remember, you can only calculate enthalpy of reaction changes from bond enthalpies if all the
species are gaseous!

(c) If the enthalpy of vapourisation of water is +40.7 kJmol -1 and the enthalpy of vapourisation
of cyclohexane is +30.0 kJmol-1, from your answer to (b), recalculate the enthalpy of
combustion of cyclohexane.

You need to think about which state changes are endothermic and which state changes are
exothermic!

(d) Compare and comment on your answers to (a), (b) and (c) and, where appropriate, quote
percentage errors.

ANSWERS to the ΔH enthalpy Q's  *  Thermochemistry and Enthalpy Notes

 
Question 4

(a) Given the following standard enthalpies of combustion ΔHθc (298K, 1 atm)

C(s) -393 kJmol-1; H2(g) -285.6 kJmol-1;

and the enthalpy of formation of ethanoic acid, ΔHθf(CH3COOH(l)) = -487 kJ mol-1

Calculate the standard enthalpy of combustion of ethanoic acid, ΔH θc(CH3COOH(l))

(b) Using the bond enthalpies listed in Q1(c), and assuming all reactants and products are
gases, calculate the enthalpy of combustion of ethanoic acid, noting that the bond enthalpy for
C=O is +743 kJmol-1 when it is NOT in the carbon dioxide molecule.

(c) If the enthalpy of vaporisation of ethanoic acid is 51.6 kJmol -1 and the enthalpy of
vaporisation of water is 40.7 kJmol-1, use your answer from (b) to calculate the enthalpy of
combustion of ethanoic acid under standard conditions, ie a corrected value to take into
account the standard states of reactants and products at 298K/1atm.

(d) Compare and comment on the three values of ΔHcomb(ethanoic acid) calculated in parts (a),
(b) and (c).

ANSWERS to the ΔH enthalpy Q's  *  Thermochemistry and Enthalpy Notes

 
Question 5

Given the following standard enthalpies of formation ΔHθf(298K, 1 atm)

NH3(g) -46.2 kJmol-1; HCl(g) -92.3 kJmol-1; NH4Cl(s) -315.0 kJmol-1

Calculate the standard enthalpy change for the reaction, ΔHθr

NH4Cl(s) ====> NH3(g) + HCl(g)

ANSWERS to the ΔH enthalpy Q's  *  Thermochemistry and Enthalpy Notes

 
Question 6

Given the following standard enthalpies of formation,  ΔHθf, in kJmol-1 (298K, 1 atm)

CH4(g) -74.9; CH3Br(l) -36.0; HBr(g) -36.2

Calculate the standard enthalpy change for the reaction, ΔHθr

Br2(l) + CH4(g) ====> CH3Br(l) + HBr(g)

ANSWERS to the ΔH enthalpy Q's  *  Thermochemistry and Enthalpy Notes

Question 7

(a) Define the term 'average bond enthalpy'.

(b) Given the following standard enthalpies of formation, ΔHθf in kJmol-1 (298K, 1 atm)

C3H8(g) -104 ; C3H7Cl(g) -105 ; HCl(g) -92

Calculate the standard enthalpy change for the reaction, ΔHθr

Cl2(g) + C3H8(g) ====> C3H7Cl(g) + HCl(g)

(c) Given the following average bond energies in kJmol-1

bond ΔHBE: C-H 412 ; Cl-Cl 242 ; C-Cl 338 ; H-Cl 431

Calculate the enthalpy change for the same reaction as in (b)

(d) Explain which of the calculations in (b) or (c) will be the most accurate and why?

ANSWERS to the ΔH enthalpy Q's  *  Thermochemistry and Enthalpy Notes

Question 8

(a) Given the following standard enthalpies of formation, ΔHθf in kJ mol-1 at 298K, 1 atm

C2H6(g) -84.7 ; C2H5I(l) -39.1 ; HI(g) +25.9

Without using a Hess's Law Cycle, calculate the standard enthalpy change, ΔHθr for the
reaction:

C2H6(g) + I2(s) ====> C2H5I(l) + HI(g)

(b) Given the following average bond energies in kJ mol -1

bond ΔHBE: C-H 412 ; C-I 228 ; H-I 299,

 and the enthalpy of vapourisation of iodoethane is 32.0 kJmol -1,

and the enthalpy of atomisation of iodine is 107 kJmol-1,

calculate the enthalpy change for the same reaction in (a) by any method you choose!

(c) How do your answers to (a) and (b) compare?

ANSWERS to the ΔH enthalpy Q's  *  Thermochemistry and Enthalpy Notes

Question 9

Given the bond enthalpies (ΔHBE) in kJ mol-1: C-H 412, C-C 348 and H-H 436 (∆Hatom = 218 kJ
mol-1).

Calculate the enthalpy of formation of propane if the enthalpy of atomisation of carbon

(graphite) is 715kJ mol-1.
 Q1(c)(ii) Apart from the fact that bond enthalpy values are
typical/average values in a variety of similar molecules, the
bigger source of error is that the calculation in (c) does NOT take
into account the enthalpy of vaporisation of water. Extra energy
would be released from the condensation of water, giving a more
exothermic value ie closer to -1560 kJmol-1.

NOTE: Since the enthalpy of vapourisation of water is 40.7 kJmol -1, 3 x

40.7 kJ would be released when the water condenses, giving an
enthalpy of combustion of -1442 -(3 x 40.7) = -1564 kJmol -1, which is
very close to the standard value. See Questions 3, 4 and 8 for
examples of comparing standard enthalpy of reaction values with
those calculated from bond enthalpies.

Original set of Questions  *  Thermochemistry and Enthalpy Notes

 
 Original set of Questions

Answers to Questions 3 and 4

Q3(c) to apply a 'correction' to your answer to Q3(b) you need to

allow for the endothermic vapourisation of 1 mole of cyclohexane
and the exothermic condensation of 6 moles of water, therefore ...

ΔHcomb(corrected) = ΔHcomb(via bond enthalpies) +

ΔHvap(cyclohexane) - 6 x ΔHvap(water)
 ΔHcomb(corrected) = -3720 + 30.0 - 6 x 40.7 = -3934.2 kJmol-1

(d) Calculation (a) gave a value of -3915.6 kJmol-1 for the standard
enthalpy of combustion of cyclohexane (298K/1atm).

(a) Apart from (a) none of the answers can be considered as a

standard enthalpy values at 298K/1 atm, since bond enthalpy
calculations can only involve gaseous species and the fact that
bond energies are based on average/typical values for similar
molecules.

(b) The value of -3720 kJmol-1, ignoring state changes, has an

error of 195.6 kJmol-1 compared to the standard enthalpy value
based on standard enthalpy changes calculated in (a). This is
~5% error, hardly insignificant!

(c) When corrections are applied to take into account state

changes with respect to 298K/1 atm. the error is reduced to 18.6
kJmol-1 (~0.5%), and not a bad result from typical/average bond
enthalpies in organic molecules

Q3(c) to apply a 'correction' to your answer to Q3(b) you need to

allow for the endothermic vapourisation of 1 mole of cyclohexane
and the exothermic condensation of 6 moles of water, therefore ...

ΔHcomb(corrected) = ΔHcomb(via bond enthalpies) +

ΔHvap(cyclohexane) - 6 x ΔHvap(water)

ΔHcomb(corrected) = -3720 + 30.0 - 6 x 40.7 = -3934.2 kJmol-1

(d) Calculation (a) gave a value of -3915.6 kJmol-1 for the standard
enthalpy of combustion of cyclohexane (298K/1atm).

(a) Apart from (a) none of the answers can be considered as a

standard enthalpy values at 298K/1 atm, since bond enthalpy
calculations can only involve gaseous species and the fact that
bond energies are based on average/typical values for similar
molecules.

(b) The value of -3720 kJmol-1, ignoring state changes, has an

error of 195.6 kJmol-1 compared to the standard enthalpy value
based on standard enthalpy changes calculated in (a). This is
~5% error, hardly insignificant!

(c) When corrections are applied to take into account state

changes with respect to 298K/1 atm. the error is reduced to 18.6
kJmol-1 (~0.5%), and not a bad result from typical/average bond
enthalpies in organic molecules

Original set of Questions  *  Thermochemistry and Enthalpy Notes

  

Q4(c) ΔHcomb(corrected) = ΔHcomb(via bond enthalpies) +

ΔHvap(ethanoic acid) - 2 x ΔHvap(water)

ΔHcomb(corrected) = -932 +51.6 - 2 x 40.7 = -3934.2 kJmol -1 = -961.8

kJmol-1

(d) Unlike in Q3, the corrected bond energy enthalpy value does
not give a more accurate one, than that based solely on the bond
enthalpies of gaseous species. In fact, applying the correction,
actually makes the value even further from the standard enthalpy
change calculated in (a)

I'm not sure why these bond enthalpy calculations are so

'inaccurate' (~7% and ~11%), but there is some uncertainty in the
bond energies eg I could not find C-O and C=O bond energies for
a carboxylic acid and this easily make a significant difference.

Original set of Questions  *  Thermochemistry and Enthalpy Notes

Answers to Questions 5 to 7
Original set of Questions  *  Thermochemistry and Enthalpy Notes

Answers to Question 8

Q8(a) ΔHθreaction,298K = ∑ΔHθf,298(products) - ∑ΔHθf,298(reactants)

 C2H6(g) + I2(s) ==> C2H5I(l) + HI(g)

ΔHθreaction,298K = {ΔHθf,298(iodoethane) + ΔHθf,298(hydrogen iodide)} -

(ΔHθf,298(ethane)

ΔHθreaction,298K = -39.1 +25.9 +84.7 = +71.5 kJmol-1

(b)

Endothermic changes

to atomise one mole of iodine = 2 x +107 = +214 kJ (remember

atomisation refers to 1 mol atoms)

breaking one C-H bond = +412 kJ

total = +626 kJ

Exothermic changes

one C-I bond formed = -228

one HI bond formed = -299

condensation of 1 mole iodoethane = -32

total = -559

Overall enthalpy change ΔHreaction = +626 -559 = +67 kJmol-1

(c) The two values are reasonably close with an error of 4.5kJ in
(b) compared to the standard enthalpy of reaction value.

NOTE: The error of ~6% is quite significant BUT if any of the bond
energy values are out by a few kJ, then an error of that magnitude
readily results.

Original set of Questions  *  Thermochemistry and Enthalpy Notes

Answers to Question 9

Q9   Calculating the enthalpy of formation of propane from bond energy

data and ∆Hsub(carbon)
Don't forget to change the positive signs for bond enthalpies of dissociation into
negative values of bond formation.

3C(s) + 4H2(g) C3H8(g)

ΔHsub(C(s)) + 4 x 2 x ΔHbond form(C-C(g)) + 8
ΔHbond diss(H2(g)) x ΔHbond form(C-H(g))

= (3 x 715) + (4 x (2 x -348) + (8 x -412)

436) =

= 2145 +  1744 = = -696 - 3296 = -3992

+3889 kJ kJ
3C(g) + 8H(g)
∆Hform(C3H8) = +3889 + (-3992) =  -103 kJ mol-1 (data book value -104 kJ mol-1)