Energetics – Part 1

1. Definitions of standard enthalpy of

neutralisation, combustion, formation and
atomisation
2. Hess’s Law and enthalpy cycle calculation
3. Bond enthalpy and mean bond enthalpy
Energetics – energy level diagram
Exothermic reaction Endothermic reaction

reactants products
Energy

Energy
H < 0 H > 0
products
reactants

progress of reaction progress of reaction

 Exothermic vs Endothermic
Exothermic Endothermic

energy is released energy is absorbed

H is negative H is positive

bond forming is exothermic bond breaking is endothermic

energy released > energy absorbed energy needed > energy absorbed

temperature rises temperature drops

energetically favoured energetically disfavoured

 Calorimetry
q = mcΔT
• q = heat energy (J)
• m= mass of water (g)
• c = specific heat capacity of water
• = 4.18 J g-1 K-1
• ΔT = temperature change (K)
−𝐪
ΔH =
𝐧
n = the moles of the limiting reagent used (mol)
For example
• the fuel in burner for combustion
• the acid/alkali for neutralisation
• the metal for displacement
• the salt for dissolving in water
 Calorimetry
Source of errors
1. Incomplete combustion
(for combustion only)
Less heat energy is released from
burning fuel.
The experimental ΔH is less
exothermic

2. Heat loss (if no insulation provided)

Less heat energy is transferred to water.
The experimental ΔH decreases
 Calorimetry
Source of errors
3. Fuel is evaporated
(for combustion only)
The moles of fuel calculated is
more than those actually burned.
The experimental ΔH is less
exothermic

4. The heat capacity of container is not taken into account

The calculated q is smaller than the actual value
The experimental ΔH is less exothermic
 Definition
• Standard enthalpy change of reaction ΔHr⊖
(⊖ = standard condition:298K and 101 kPa or 1 atm)
Enthalpy change measured at 298K and 101 kPa which
occurs when the molar quantities of substances react as
specified in the balanced equation

Equations to represent ΔHr⊖

N2(g) + 3H2(g) → 2NH3(g) ΔHr⊖ = -92 kJ mol-1
0.5N2(g) + 1.5H2(g) → NH3(g) ΔHr⊖ = -46 kJ mol-1
2N2(g) + 6H2(g) → 4NH3(g) ΔHr⊖ = -184 kJ mol-1

ΔHr⊖ changes as molar quantities in balanced eqaution change

 Definition
• Standard enthalpy change of neutralisation ΔHneut⊖
Enthalpy change measured at 298K and 101 kPa when one
mole of water is formed by neutralisation of an acid and an
alkali

Equations to represent ΔHneut⊖

NaOH(aq) + HCl(aq) → H2O(l) + NaCl(aq)

NaOH(aq) + 0.5H2SO4(aq) → H2O(l) + 0.5Na2SO4

Equations are required to scale to 1 molar quantity of H2O(l) for one mole
of water formed in definition
 Definition
• Standard enthalpy change of combustion ΔHc⊖
Enthalpy change measured at 298K and 101 kPa when one
mole of substance is completely burned in oxygen.

Equations to represent ΔHc⊖ always exothermic

C(s) + O2(g) → CO2(g)
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
C3H6(g) + 4.5O2(g) → 3CO2(g) + 3H2O(l)

Scale to 1 molar quantity of fuel substance completely burned

Complete combustion
States of matter are in standard conditions (298K, 101 kPa)
 Definition
• Standard enthalpy change of formation ΔHf⊖
Enthalpy change measured at 298K and 101 kPa when one
mole of compound is formed from its elements in their standard
states
Exothermic for stable compound
Equations to represent ΔHf⊖ Endothermic for less stable compound

C(s) + O2(g) → CO2(g)

same as to represent ΔHc⊖, ΔHc⊖(C) = ΔHf⊖(CO2)

C(s) + 2H2(g) + 0.5O2(g) → CH3OH(l)

Ca(s) + C(s) + 1.5O2(g) → CaCO3(s)
Scale to 1 molar quantity of compound formed
States of matter are in standard conditions (298K, 101 kPa)
 Definition
• Standard enthalpy change of formation ΔHf⊖
Enthalpy change measured at 298K and 101 kPa when one
mole of compound is formed from its elements in their
standard states

ΔHf⊖ of element is always equal to 0, since the reactants and products

is identical in the same state
For example
O2(g) → O2(g)
K(s) → K(s)
 Definition
• Standard enthalpy change of atomisation ΔHat⊖
Enthalpy change measured at 298K and 101 kPa when one
mole of gaseous atom is formed from its element in its
standard state

⊖
always endothermic
Equations to represent ΔHat
Na(s) → Na(g)
0.5H2(g) → H(g)
0.5Br2(l) → Br(g)
Scale to 1 molar quantity of gaseous atom
States of matter are in standard conditions (298K, 101 kPa)
 Definition summary
• Standard enthalpy change of reaction ΔHr⊖
Enthalpy change measured at 298K and 101 kPa which
occurs when the molar quantities of substances react as
specified in the balanced equation

• Standard enthalpy change of neutralisation ΔHneut⊖

Enthalpy change measured at 298K and 101 kPa when
one mole of water is formed by neutralisation of an acid
and an alkali

• Standard enthalpy change of combustion ΔHc⊖

Enthalpy change measured at 298K and 101 kPa when
one mole of substance is completely burned in oxygen
 Definition summary
• Standard enthalpy change of formation ΔHf⊖
Enthalpy change measured at 298K and 101 kPa when
one mole of compound is formed from its elements in their
standard states

• Standard enthalpy change of atomisation ΔHat⊖

Enthalpy change measured at 298K and 101 kPa when
one mole of gaseous atom is formed from its element in its
standard state
 Hess’s Law
Enthalpy change of a reaction is independent of the path
taken given that the initial and final conditions are the same

Enthalpy cycle / Hess cycle

ΔHA
Reactants Products

ΔHB ΔHD

ΔHC
Substance X Substance Y

ΔHA = ΔHB + ΔHc - ΔHD ΔHD = - ΔHA + ΔHB + ΔHc

Example 1 - Construct an enthalpy cycle with following data, and
calculate ΔHf⊖ of CO(g)
C(s) + O2(g) → CO2(g) ΔHc⊖(C) = -394 kJ mol-1
CO(g) + 0.5O2(g) → CO2(g) ΔHc⊖(CO) = -283 kJ mol-1

Step 1: Write the equation for ΔHf⊖(CO)

Step 2: Think how to construct the cycle with data provided

ΔHf⊖(CO)
C(s) + 0.5O2(g) CO(g)

+ 0.5O2(g) ΔHc⊖(C) ΔHc⊖(CO) + 0.5O2(g)

CO2(g)
 Example 1 - Construct an enthalpy cycle with following data, and
calculate ΔHf⊖ of CO(g)
C(s) + O2(g) → CO2(g) ΔHc⊖(C) = -394 kJ mol-1
CO(g) + 0.5O2(g) → CO2(g) ΔHc⊖(CO) = -283 kJ mol-1

ΔHf⊖(CO)
C(s) + 0.5O2(g) CO(g)

+ 0.5O2(g) ΔHc⊖(C) ΔHc⊖(CO) + 0.5O2(g)

CO2(g)

Step 3: calculate ΔHf⊖(CO)

ΔHf⊖(CO) = ΔHc⊖(C) - ΔHc⊖(CO) = -394 –(–283) = -111 kJ mol-1
 Example 2 - Construct an enthalpy cycle with following data, and
calculate ΔHf⊖ of CH4(g)

ΔHc⊖(C) = -394 kJ mol-1 C(s) + O2(g) → CO2(g)

ΔHc⊖(H2) = -286 kJ mol-1 H2(g) + 0.5O2(g) → H2O(l)
ΔHc⊖(CH4) = -890 kJ mol-1 CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
You may need to write equations yourselves!

ΔHf⊖(CH4)
C(s) + 2H2(g) CH4(g)

+ O2(g) ΔHc⊖(C) ΔHc⊖(CH4)

+ 2O2(g)
+O2(g) 2ΔHc⊖(H2)

CO2(g) + 2H2O(l) You need to double ΔHc⊖(H2) as to

satisfy the molar quantities in equation
 Example 2 - Construct an enthalpy cycle with following data,
and calculate ΔHf⊖ of CH4(g)
ΔHc⊖(C) = -394 kJ mol-1 C(s) + O2(g) → CO2(g)
ΔHc⊖(H2) = -286 kJ mol-1 H2(g) + 0.5O2(g) → H2O(l)
ΔHc⊖(CH4) = -890 kJ mol-1 CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)

ΔHf⊖(CH4)
C(s) + 2H2(g) CH4(g)

+ O2(g) ΔHc⊖(C) ΔHc⊖(CH4)

+ 2O2(g)
+ O2(g) 2ΔHc⊖(H2)

CO2(g) + 2H2O(l)
ΔHf⊖(CH4)
= [ΔHc⊖(C) + 2ΔHc⊖(H2)] - ΔHc⊖(CH4) = [-394 + 2(-286)] -(-890)
= -76 kJ mol-1
 Example 3 - Construct an enthalpy cycle with following data,
and calculate ΔHf⊖ of C2H5OH(l)
ΔHc⊖(C) = -394 kJ mol-1 C(s) + O2(g) → CO2(g)
ΔHc⊖(H2) = -286 kJ mol-1 H2(g) + 0.5O2(g) → H2O(l)
ΔHc⊖(C2H5OH) = -1367 kJ mol-1
C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(l)

ΔHf⊖(C2H5OH)
2C(s) + 3H2(g) + 0.5O2(g) C2H5OH(l)

2ΔHc⊖(C) ΔHc⊖
+3O2(g) 3ΔcH⊖(H2) (C2H5OH) +3O2(g)

2CO2(g) + 3H2O(l)

To complelely burn 2C(s) and 3H2(g), 3.5O2(g) are needed

However 0.5O2(g) is already present, extra 3O2(g) is added
Example 3
ΔHc⊖(C) = -394 kJ mol-1 ΔHc⊖(H2) = -286 kJ mol-1
ΔHc⊖(C2H5OH) = -1367 kJ mol-1
ΔHf⊖(C2H5OH)
2C(s) + 3H2(g) + 0.5O2(g) C2H5OH(l)

2ΔHc⊖(C) ΔHc⊖
+3O2(g) 3ΔHc⊖(H2) (C2H5OH) +3O2(g)

2CO2(g) + 3H2O(l)
ΔHf⊖(C2H5OH) = [2(-394) + 3(-286)] - (-1367) = -279 kJ mol-1

Any enthalpy change data of O2(g) is unnecessary.

1. O2 is incombustible so ΔHc⊖(O2) is senseless.
2. ΔHf⊖(O2) = 0 since O2 is an element.
Example 4 - Construct an enthalpy cycle with following data, and
calculate ΔHr⊖ of following reaction
AlCl3(s) + 6H2O(l) → AlCl3•6H2O(s)

ΔHf⊖(AlCl3) = -704 kJ mol-1 Al(s) + 1.5Cl2(g) → AlCl3(s)

ΔHf⊖(H2O) = -286 kJ mol-1 H2(g) + 0.5O2(g) → H2O(l)
ΔHf⊖(AlCl3•6H2O) = -2692 kJ mol-1
Al(s) + 1.5Cl2(g) + 6H2(g) + 3O2(g) → AlCl3•6H2O(s)

ΔHr⊖
AlCl3(s) + 6H2O(l) AlCl3•6H2O(s)

ΔHf⊖
ΔHf ⊖(AlCl
3)
(AlCl3•6H2O)
6ΔHf⊖(H2O)

Al(s) + 1.5Cl2(g) + 6H2(g) + 3O2(g)

ΔHr⊖= -[-704 + 6(-286)] + (-2692) = -272 kJ mol-1

Example 5 - Construct an enthalpy cycle with following data, and
express ΔH1 in terms of ΔH2 and ΔH3
2NaHCO3(s) → Na2CO3(s) + H2O(l) + CO2(g) ΔH1
NaHCO3(s) + HCl(aq) → NaCl(aq) + H2O(l) + CO2(g) ΔH2
Na2CO3(s) + 2HCl(aq) → 2NaCl(aq) + H2O(l) + CO2(g) ΔH3

ΔH1
2NaHCO3(s) Na2CO3(s) + H2O(l) + CO2(g)

2ΔH2 ΔH3
+ 2HCl(aq)
+ 2HCl(aq)

2NaCl(aq) + 2H2O(l) + 2CO2(g)

ΔH1= 2ΔH2 –
ΔH3
Example 6 - Construct an enthalpy cycle with following data, and
calculate ΔHr⊖ of following reaction
2Li(s) + 2H2O(l) → 2Li+(aq) + 2OH-(aq) + H2(g)
Li(s) + 0.5H2(g) + 0.5O2(g) → LiOH(s) ΔHf⊖(LiOH) = -485 kJ mol-1
H2(g) + 0.5O2(g) → H2O(l) ΔHc⊖(H2) = -286 kJ mol-1
LiOH(s) → Li+(aq) + OH-(aq) ΔHsol⊖(LiOH) = -21 kJ mol-1

ΔHr⊖
2Li(s) + 2H2O(l) 2Li+(aq) + 2OH-(aq) + H2(g)

2ΔHf⊖(LiOH) 2ΔHc⊖(H2)
+ H2(g) 2ΔHsol⊖(LiOH)
+ H2(g)
+ O2(g) + O2(g)

2LiOH(s) + H2(g)
 ΔHr⊖
2Li(s) + 2H2O(l) 2Li+(aq) + 2OH-(aq) + H2(g)

2ΔHf⊖(LiOH)
+ H2(g)
+ O2(g) = 2(-485) kJ/mol

2LiOH(s) + 2H2O(l) 2ΔHsol⊖(LiOH)

= 2(-21) kJ/mol
2ΔHc⊖(H2)
+ H2(g)
+ O2(g) = 2(-286) kJ/mol

2LiOH(s) + H2(g)

ΔHr⊖= 2(-485) – 2(-286) + 2(-21) = -440 kJ mol-1

 Bond enthalpy ΔHB
Enthalpy change when one mole of bond in the gaseous
state is broken
X-Y(g) → X(g) + Y(g) ΔHB(X-Y)

Equations
HCl(g) → H(g) + Cl(g) ΔHB(H-Cl)

Cl2(g) → 2Cl(g) ΔHB(Cl-Cl)

1
NB 0.5Cl2(g) → Cl(g) ΔHat(Cl) = 2ΔHB(Cl-Cl)

H2(g) → 2H(g) ΔHB(H-H) = 2ΔHat(H)

Scale to 1 molar quantity of bond broken

All species in gaseous state
 ΔHB(N-H)

+394 kJ mol-1

+391 kJ mol-1

+388 kJ mol-1

NH3(g) → N(g) + 3H(g) ΔHr = 394 + 391 + 388

= +1174 kJ mol-1
= enthalpy change to break down all N-H bond in one mole of NH3

Mean bond enthalpy of N-H bond in NH3

E(N-H) = +1173 / 3 = +391 kJ mol-1
 Mean bond enthalpy
Enthalpy change when one mole of bond in the gaseous
state is broken, averaged over different molecules

Example 1
CH4(g) → C(g) + 4H(g) ΔHr = +1663 kJ mol-1
Mean bond enthalpy of C-H bond in CH4
E(C-H) = +1663 / 4 = +415.75 kJ mol-1

Example 2
H-O-H(g) → O-H(g) + H(g) ΔH = +496 kJ mol-1
O-H(g) → O(g) + H(g) ΔH = +432 kJ mol-1
Mean bond enthalpy of O-H bond in H2O
E(O-H) = (+496+432) / 2 = +464 kJ mol-1
 Example 3
Use the following data to calculate the E(S-F) in SF6
ΔHf⊖(SF6) = -1100 kJ mol-1 S(s) + 3F2(g) →SF6(g)
ΔHat⊖(S) = +223 kJ mol-1 S(s) → S(g)
E(F-F) = 158 kJ mol-1 F2(g) → 2F(g)

Equation for breaking six S-F bonds: SF6(g) → S(g) + 6F(g)

ΔHr⊖
SF6(g) S(g) + 6F(g)

ΔHat⊖(S)
ΔHf ⊖(SF
6)
3E(F-F)
S(s) + 3F2(g)

ΔHr⊖= -(-1100) + [223 + 3(158)] = +1797 kJ mol-1

E(S-F) = +1797 / 6 = +299.5 kJ mol-1
 WS
Example 4 Calculate the ΔHr for 2H2O2(g) → 2H2O(g) + O2(g)p. 4

Bond H-O O-O O=O

E(bond) /kJ mol-1 464 146 498

ΣE(bond broken) ΣE(bond formed)

= 2[ (O-O) + 2(H-O) ] = 2 x 2(O-H) + (O=O)
= 2(146 + 2 x 464) = 2 x 2 x 464 + 498
= 2148 kJ mol-1 = 2354 kJ mol-1
endo exo
ΔHr = ΣE(bond broken) - ΣE(bond formed)
= 2148 - 2354
= -206 kJ mol-1 (exothermic)