Chemistry

Lecture 15 By: Syed Ali Shan

Chemical Energetics
Outline:

Concept of Energy changes during Chemical reactions

Use the terms;
 Enthalpy change of reaction
 Bond energy
Numerical Magnitude of Lattice energy
Hess’s law to construct simple energy cycles

Thermo-chemistry

 Based on 1st law of thermodynamics

 Study of heat changes during chemical reaction

Thermo-chemical Equation:

 Gives the values of heat changes during reaction (measured in terms of the enthalpy changes 
∆H)
 The equation that gives physical states of reactants and products
 When a chemical equation is reversed, the magnitude of the ∆H remains same but its sign is
reversed
 The coefficients of various substances of chemical equation represents the number of their
respective moles
 If coefficients in the chemical equation are multiplied or divided by some number, the ∆H value
must also be multiplied or divided by the same number

Exothermic Reactions Endothermic Reactions

Heat evolved by system Heat absorbed by system
∆H = negative ∆H = positive
Temperature of system first rises, then becomes equal to Temperature of system first decreases, then becomes equal
room temperature to room temperature
Extra heat travels to surrounding there by increasing ‘T’ of Heat travels from surrounding to system, so ‘T’ of
surrounding surrounding decreases
Heat travels from system to surrounding Heat travels from surrounding to system
No. of bond formed is greater than bond breakage No. of bond formed is lesser than bond breakage
Most spontaneous reactions are exothermic Most non-spontaneous reactions are endothermic
Enthalpy content of reactant is higher than product i.e. Enthalpy content of reactant is lower than product i.e.
HR > HP HR < HP
Products are more stable than reactants Reactants are more stable than products
C(s) + O2(g) → CO2(g) ∆H = -393.7 kjmol-1 N2(g) + O2(g) → 2NO (g) ∆H = +180.5 kjmol-1
Process of Respiration Photosynthesis and Evaporation

System:

 Anything under consideration/experimentation

Surrounding:

 Everything except the system

 Equilibrium b/w system and surrounding gives reversible
reactions

Boundary:

 Imaginary line separating system from surrounding

State Function:

 Macroscopic property of system

 Has initial and final states
 Independent of path followed to bring the change
 Examples: Pressure, Temperature, Volume, Internal energy (E), Enthalpy (H),Entropy (S), Gibbs
free energy (G) [∆G > 0 (non-spontaneous process), ∆G < 0 (spontaneous process), ∆G = 0
(process at equilibrium)]
 Their absolute values aren’t measured but change is measured (∆E = E2 – E1)

Modes of Transference of Energy:

Heat (q) Work (w)

Energy that flows across the boundary of a system It is defined as the product of force and distance.
during a change in its state due to the difference in In thermo-chemistry, we study pressure-volume
temperature between the system and the work
surroundings. (random form of energy)
It occurs when there is difference in temperature Occurs if system involves gaseous substances and
b/w system and surrounding there is pressure difference b/w system and
surrounding
Not a state function so path dependent (so q = q1 + Not a state function so path dependent (so w = w1
q2 + q3 +……….) + w2 + w3 +……….)
Units; J, kJ, Calories Units; J, ergs (CGS system)
q = +ve (Heat absorbed by system) w = +ve (Work done on system)
q = -ve (Heat evolved by system) w = -ve (Work done by system)
(q + w) is a state function

1st Law of Thermodynamics

 Also called the law of conservation of energy

 States that energy can neither be created nor destroyed, but can be changed from one form to
another
 Internal energy (sum of all possible energies i.e. K.E + P.E) change is given as;
∆E = q + w
∆E = q - P∆V (work done by system to move piston upwards, so w = - P∆V)
∆E = qv – P(0) (∆V = 0, as volume is constant)
∆E = qv
 This shows that a change in internal energy of a system, at constant volume is equal to heat
absorbed by the system (qv)
 Enthalpy (H):
 Total heat content of system
 Enthalpy is equal to the internal energy, E plus the product of pressure and volume (PV)
H = E + PV
∆H = ∆E + ∆(PV)
∆H = ∆E + P∆V + V∆P
∆H = ∆E + P∆V + V(0) (∆P = 0, as P is constant)
∆H = ∆E + P∆V (For Gases) (i) [∆H ≈ ∆E for liquids/solids as no V changes]
∆H = q - P∆V + P∆V
∆H = qp
 This shows that change in enthalpy is equal to heat of reaction at constant pressure
 q p > qv
Energy Change of Reaction

Standard conditions:

 1 mole, 250C (298 k), 1 atm

Important Terms:

 ∆H = HP - HR
 ∆H0 = standard enthalpy change
 ∆E = internal energy change
  ∆S = entropy change
 ∆G = free energy change

Enthalpy of Reaction (∆H0r):

 Depends upon;
i. Physical states of reactants and products
ii. Temperature during reaction
iii. Pressure during reaction
iv. Quantities (moles) of reactant/product
v. Nature of the reactants
 Amount of heat evolved or absorbed when certain number of moles of reactant react
completely to give product under standard conditions
H2 (g) + 1/2O2 (g) → H2O (ℓ) ∆H = -285.8 kjmol-1

Enthalpy of Formation (∆H0f):

 For compounds
 Amount of heat evolved or absorbed when 1 mole of compound is formed from its elements
under standard conditions
Mg (s) + 1/2O2 (g) → MgO (s) ∆H0f = -692 kjmol-1
C (s) + O2 (g) → CO2 (g) ∆H0f = -393.7 kjmol-1

Enthalpy of Atomization (∆H0at):

 For elements
 Amount of heat absorbed when 1 mole of gaseous atom is formed from its element under
standard conditions
1/2H2 (g) → H (g) ∆H0at = +218 kjmol-1

Enthalpy of Neutralization (∆H0n):

 For acid-base reactions

 Amount of heat evolved when 1 mole of H+ (from acid) reacts with 1 mole of OH- (from base) to
form 1 mole of water under standard conditions
H+ (aq) + OH- (aq) ⇌ H2O (ℓ) ∆H0n = -57.4 kjmol-1 [for strong acid-base]

Enthalpy of Combustion (∆H0c):

 For substances (either element or compound)

 Amount of heat evolved when 1 mole of substance is burnt completely in excess of oxygen
under standard conditions
C2H5OH (ℓ) + 3O2 (g) → 2CO2 (g) + 3H2O (ℓ) ∆H0c = -1368 kjmol-1

C (s) + O2 (g) → CO2 (g) ∆H0c = -393.7 kjmol-1

Enthalpy of Solution (∆H0sol.):

 For solutions
 Amount of heat evolved or absorbed when 1 mole of substance is dissolved in so much solvent
that further dilution results no detectable heat change under standard conditions
 Ammonium chloride  ∆H0sol. = +16.2 kjmol-1
 Sodium carbonate  ∆H0sol. = -25 kjmol-1

Bond Energy: (Already discussed in Lecture of Chemical bonding)

Measurement of ∆H0:

Experimentally by calorimeters Calculated by Hess’s Law

Glass Calorimeter Bomb Calorimeter Applicable for;
∆H0n is measured ∆H0c is measured i. One step reaction
0 0
∆H n = q = m × s × ∆T ∆H c = q = c × ∆T ii. For multi step reactions (specially)
q = heat evolved c = heat capacity (heat ∆H = ∆H1 + ∆H2 + ∆H3
m = mass of substance required to change ‘T’
S = specific heat(JK-1g-1) by 1 K) Born-Haber cycle is application of Hess’s
∆T = ‘T’ change law used for ionic compounds
Calorimeters only applicable for 1 step reactions
Solve Relevant Numerical as Precaution

Hess’s Law (Q.16, Q.17, Q.18, Q.19, Q.20)

 If a chemical change takes place by several different routes, the overall energy change is the
same, regardless of the route by which the chemical change occurs, provided the initial and final
conditions are the same

 ∆H for many compounds cannot be measured directly from calorimeter like;

 CCl4 cannot be prepared directly by combining carbon and chlorine. Similarly, it does not
decompose easily into its constituent elements.
 Boron oxide (B2O3) and aluminium oxide (Al2O3) form protective layer of oxides covers
the surface of the unreacted element.
 Formation of CO cannot be measured directly due to the formation of CO 2 with it.
Enthalpy of formation of CO:

C (graphite) + O2 (g) → CO2 (g) ∆H = - 393.7 kjmol-1

CO (g) + 1/2O2 (g) → CO2 (g) ∆H1 = - 283 kjmol-1
C (graphite) + 1/2O2 (g) → CO (g) ∆H2 = ?
∆H = ∆H1 + ∆H2
- 393.7 = - 283 + ∆H2
∆H2 = - 393.7 + 283 = - 110.7 kjmol-1

Formation of Sodium carbonate: verification of Hess’s law

Single step process:

2NaOH (aq) + CO2 (g) → Na2CO3 (aq) + H2O (ℓ) ∆H = - 89.08 kjmol-1
Two step process:
NaOH (aq) + CO2 (g) → NaHCO3 (aq) ∆H1 = - 48.06 kjmol-1
NaOH (aq) + NaHCO3 (aq) → Na2CO3 (aq) + H2O (ℓ) ∆H2 = - 41.02 kjmol-1

∆H = ∆H1 + ∆H2
- 89.08 = - 48.06 + (-41.02)
- 89.08 = - 89.08

Applications:

 Heat of combustion
 Heat of formation
 Indirect enthalpy change measurements
 Lattice energy (Born-Haber cycle)

Q.16: By applying Hess’s law, calculate the enthalpy change for the formation of an aqueous solution of
NH4Cl from NH3 gas and HCl gas. The results for the various reactions are as follows;

NH3 (g) + aq → NH3 (aq) ∆H = - 35.16 kjmol-1

HCl (g) + aq → HCl (aq) ∆H = - 72.41 kjmol-1

NH3 (aq) + HCl (aq) → NH4Cl (aq) ∆H = - 51.48 kjmol-1

Solution:

Path 1 (Direct route as asked in question)

NH3 (g) + HCl (g) → NH4Cl (aq) ∆H = ?
Path 2 (Indirect route as given in question)

NH3 (g) + aq → NH3 (aq) ∆H1 = - 35.16 kjmol-1

HCl (g) + aq → HCl (aq) ∆H2 = - 72.41 kjmol-1

 NH3 (aq) + HCl (aq) → NH4Cl (aq) ∆H3 = - 51.48 kjmol-1

∆H = ∆H1 + ∆H2 + ∆H3

∆H = (- 35.16) + (-72.41) + (- 51.48) = - 159.05 kjmol-1

Q.17: Calculate the heat of formation of ethyl alcohol from the following information;

i. Heat of combustion of ethyl alcohol is - 1367 kjmol-1

ii. Heat of formation of carbon dioxide is – 393.7 kjmol-1
iii. Heat of formation of water is – 285.8 kjmol-1

Solution:

Heat of combustion of ethyl alcohol is - 1367 kjmol-1

C2H5OH + 3O2 → 2CO2 + 3H2O ⇢ i ∆H = -1367 kjmol-1

Heat of formation of carbon dioxide is – 393.7 kjmol-1

C + O2 → CO2 ⇢ ii ∆H = -393.7 kjmol-1

Heat of formation of water is – 285.8 kjmol-1

H2 + 1/2O2 → H2O ⇢ iii ∆H = -285.8 kjmol-1

Requirement is heat of formation of ethyl alcohol;

2C + 3H2 + 1/2O2 → C2H5OH ∆H = ?

Multiply eq. (ii) with 2, eq. (iii) with 3 and then add them

2C + 2O2 → 2CO2 ⇢ ii ∆H = 2(-393.7 kjmol-1) = -787.4 kjmol-1

3H2 + 3/2O2 → 3H2O ⇢ iii ∆H = 3(-285.8 kjmol-1) = -857.4 kjmol-1

2C +3H2 + 7/2O2 → 2CO2 + 3H2O ⇢ iv ∆H = -1644.8 kjmol-1

Invert eq. (i) [when eq. is inverted sign of ∆H changes] and add it to eq. (iv)

2CO2 + 3H2O → C2H5OH + 3O2 ∆H = +1367 kjmol-1

2C +3H2 + 7/2O2 → 2CO2 + 3H2O ∆H = -1644.8 kjmol-1

2C + 3H2 + 1/2O2 → C2H5OH ∆H = - 277.8 kjmol-1

 SHORT CUT

C2H5OH + 3O2 (∆H not given) → 2CO2 + 3H2O

-1367 kjmol-1 + ∆H (as for alcohol) = 2(-393.7 kjmol-1) + 3(-285.8 kjmol-1)

∆H = -787.4 kjmol-1 + (-857.4 kjmol-1) + 1367 kjmol-1

∆H = - 277.8 kjmol-1

Q.18: If the heats of combustion of C2H4, H2 and C2H6 are -337.2, -68.3 and -372.8 k calories respectively,
then calculate the heat of the following reaction; C2H4 + H2 → C2H6

Solution:

Heat of combustion of C2H4;

C2H4 + 3O2 → 2CO2 + 2H2O ⇢ i ∆H = - 337.2 k calories

Heat of combustion of H2;

H2 + 1/2O2 → H2O ⇢ ii ∆H = - 68.3 k calories

Heat of combustion of C2H6;

C2H6 + 7/2O2 → 2CO2 + 3H2O ⇢ iii ∆H = - 372.8 k calories

Requirement is heat of formation of C2H6;

C2H4 + H2 → C2H6 ⇢ iv ∆H = ?

Add eq. (i) and eq. (ii)

C2H4 + 3O2 → 2CO2 + 2H2O ⇢ i ∆H = - 337.2 k calories

H2 + 1/2O2 → H2O ⇢ ii ∆H = - 68.3 k calories

C2H4 + H2 + 7/2O2 → 2CO2 + 3H2O ⇢ iv ∆H = - 405.5 k calories

Invert eq. (iii) [when eq. is inverted sign of ∆H changes] and add it to eq. (iv)

2CO2 + 3H2O → C2H6 + 7/2O2 ∆H = +372.8 k calories

C2H4 + H2 + 7/2O2 → 2CO2 + 3H2O ∆H = - 405.5 k calories

C2H4 + H2 → C2H6 ∆H = - 32.7 k calories

 SHORT CUT

C2H4 + H2 → C2H6

- 337.2 k calories + (- 68.3 k calories) = - 372.8 k calories + ∆H

∆H = -337.2 k calories – 68.3 k calories + 372.8 k calories

∆H = - 32.7 k calories

Q.19: Graphite and diamond are two forms of carbon. The enthalpy of combustion of graphite at 25 0C is
-393.51 kJmol-1 and that of diamond is -395.41 kJmol-1. What is the enthalpy change of the process
Graphite → Diamond at the same temperature?

Solution:

C (graphite) + O2 → CO2 ⇢ i ∆H = -393.51 kJmol-1

C (diamond) + O2 → CO2 ⇢ ii ∆H = -395.41 kJmol-1

For Graphite → Diamond, invert eq. (ii) and add with eq. (i)

C (graphite) + O2 → CO2 ∆H = -393.51 kJmol-1

CO2 → C (diamond) + O2 ∆H = +395.41 kJmol-1

C (graphite) → C (diamond) ∆H = +1.9 kJmol-1

Q.20: If the heat of neutralization of HCl and NaOH is -57.3 kJmol-1 and heat of neutralization of
CH3COOH with NaOH is -55.2 kJmol-1, calculate the enthalpy of ionization of CH3COOH.

Solution:

H+ + OH- → H2O ⇢ i ∆H = -57.3 kJmol-1

CH3COOH + OH- → H2O + CH3COO- ⇢ ii ∆H = -55.2 kJmol-1

Required:

CH3COOH → H+ + CH3COO- ∆H = ?

Invert eq. (i) and add with eq. (ii)

CH3COOH + OH- → H2O + CH3COO- ∆H = -55.2 kJmol-1

H2O → H+ + OH- ∆H = +57.3 kJmol-1

CH3COOH → H+ + CH3COO- ∆H = + 2.1 kJmol-1

 Born Haber Cycle

 Used to calculate lattice energy

 Lattice Energy: Energy released when 1 mole of ionic compound is formed from its gaseous ions
OR energy required to break 1 mole of ionic compound into its gaseous ions
 L.E ∝ charge, L.E ∝ 1/size, L.E ∝ packing of ions [NaF > NaCl > NaBr > NaI]
 Information from L.E:
 Structure of ionic solids
 Properties of ionic solids
 Strength of bonding

L.E of NaCl [Q.21 (c) on similar lines]

 Applying Hess’s law

 ∆Hf = ∆Hx + ∆Hℓ
 ∆Hℓ = ∆Hf - ∆Hx
 To find ∆Hx represents multiple enthalpy
changes, so Born Haber cycle is used for the
calculation




∆Hx = ∆Hat(Na) + ∆HI.E +∆Hat(Cl) +∆HE.A

∆Hx = +108 + 496 + 121 – 349

∆Hx = + 376 kJmol-1

 As  ∆Hℓ = ∆Hf - ∆Hx
∆Hℓ = - 411 – (+ 376)
∆Hℓ = - 787 kJmol-1