UNIT 5

Energetics

• Thermochemistry is the study of heat change in chemical reactions, usually in reference to a state of
standard state

Basic terms

1) System
A thermochemical system is defined as any portion of matter or universe under consideration, which is
separated from the rest of the universe

2) Surrounding
Everything in the universe that is not a part of the system and can interact with it is called surrounding

3) Boundary
It is anything which separates the system from its surroundings

Types of systems

4) Open system
It is a system that exchanges both energy and matter/mass with its surroundings

5) Closed system
A system which permits the exchange of energy but not matter

6) Isolated system
A system which can exchange neither energy nor matter with its surroundings
Ex – sample in a sealed thermos flask with walls made of insulating materials

7) Homogeneous system
A system in which physical state of all its matter is uniform
Ex – mixtures of gases, mixtures of completely miscible liquids

8) Heterogeneous systems
A system in which all the contents do not possess the same physical state
Ex – immiscible liquids, solids in contact with a gas

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 Properties of systems

9) Microscopic properties
A system is called a microscopic system, if it is approximately of atomic dimensions

• Properties like ………………………………………………………………………………….

will determine the microscopic properties of such systems

10) Macroscopic properties

The properties which are associated with the bulk or macroscopic state of a system
Ex -

Macroscopic properties

11) Extensive properties 12) Intensive properties

Properties that depend on the Properties that are independent
amount or size of a system of the amount or size of a system

Ex - Ex -

• Note – If any extensive property is expressed per mole (mol-1) or per gram or per cm3 it becomes
an intensive property

State of a system

• The state of a system is defined by specific, measurable macroscopic properties of the system
• The variables like P, V, T and composition, which are used to describe the state of a system are called
state variables/state functions

Ex – a gaseous mixture can be described by parameters P, V & T. When the gas is converted to a
liquid, the values of those parameters change

• State functions depend only on the initial state and the final state of the system. They do not
depend on the path by which the changes occur.

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13) Standard state

14) Spontaneous process

Processes that are occurring on their own accord. Most of them are natural and irreversible

Ex – heat flow from hotter end of a metal rod to a colder end

NaOH + HCl NaCl + H2O

15) Non-spontaneous process

They are not happening on their own accord

Ex – Although C burns in air, releasing heat to form CO2, it does not catch fire on its own. It requires
an initial heat supply

16) Reversible Processes

17) Irreversible processes

Enthalpy (H)

• Enthalpy change is the heat change thar occurs at constant pressure

• Enthalpy is an extensive property because its magnitude depends on the amount of the substance
present
• It is impossible to determine the enthalpy of a substance; therefore, we measure only the change in
enthalpy (ΔH).

Specific heat and heat capacity

• In the laboratory heat changes in physical and chemical processes are measured using a calorimeter

Specific heat capacity (s or c)

- The amount of heat required to raise the temperature of 1 g of the substance by 1 0C
- Unit -
-

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 Heat capacity (C)
- The amount of heat required to raise the temperature of a given quantity of a substance by 1 0C
- Unit -
-

Endothermic and Exothermic processes

Endothermic processes
- A system that transitions from an initial state to a final state by absorbing heat
- Reactants + E Products

Exothermic processes
- A system that transitions from an initial state to a final state by releasing heat
- Reactants Products + E

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 Standard enthalpy changes

• The standard enthalpy change of a reaction is the enthalpy change that occurs when the specified
quantities of reactants react under standard conditions to form products in their standard states

Standard conditions

Note – In thermochemical equations

1. Reactions must be balanced
2. Physical states must be mentioned (because they affect enthalpy)
3. When a chemical reaction is reversed, the value of ∆H remains same, but the sign changes
4. If the thermochemical equation is multiplied by a factor, the enthalpy change is also
multiplied by the same factor

1. Standard enthalpy change of formation

The standard enthalpy of formation (∆H!∅ ) of a substance is the enthalpy change that occurs when
one mole of the substance in its standard state is formed from the reference forms of its elements in
their standard states

For elements with allotropic forms, the reference form chosen is the more stable one, meaning the
form with the lower enthalpy

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 2. Standard enthalpy change of combustion

It is the enthalpy change when one mole of an element or compound in its standard state undergoes
complete combustion with excess O₂ under standard conditions, forming products in their standard
states.

1. Find the enthalpy change of the following reaction

3C(s,graph) + 4H2(g) C3H8(g) ∆H # = ?

C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l) ∆H # = -2219.9 kJ mol-1

C(s) + O2(g) CO2(g) ∆H # = -393.5 kJ mol-1
1/2O2(g) + H2(g) H2O(l) ∆H # = -285.8 kJ mol-1

2. Determine the enthalpy change for the decomposition reaction of sodium bicarbonate
#
2NaHCO3(s) Na2CO3(s) + H2O(l) + CO2(g) ∆H$%& =?

∆H!# NaHCO3(s) = -950.81 kJ mol-1

∆H!# Na2CO3(s). = -1130.68 kJ mol-1
∆H!# H2O(l) = -187.78 kJ mol-1
∆H!# CO2(g). = -393.5 kJ mol-1

#
3. Calculate the ∆H$%& for the combustion of C2H6(g) using the direct method
'
C2H6(g) + ( O2(g) 2CO2(g) + 3H2O(l)

∆H!# C2H6(g) = -84.7 kJ mol-1

∆H!# CO2(g) = -393.5 kJ mol-1
∆H!# H2O(l) = -285.8 kJ mol-1

4. Using the data given below, find the enthalpy change of the reaction
SO2(g) + H2O2(l) H2SO4(l)

∆H!# SO2(g) = -310 kJ mol-1

∆H!# SO3(g) = -490 kJ mol-1
) #
H2O(l) + ( O2(g) H2O2(l) ∆H$%& = -70 kJ mol-1
#
SO3(g) + H2O(l) H2SO4(l) ∆H$%& = -140 kJ mol-1

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5. Using the provided thermochemical data at 298 K, calculate the enthalpy change of the reaction
CH4(g) + H2O(g) CO(g) + 3H2(g)
)
H2(g) + ( O2(g) H2O(g) ∆H # = -242 kJ mol-1
C(s) + H2O(g) CO(g) + H2(g) ∆H # = +131 kJ mol-1
*
CH4(g) + ( O2(g) CO(g) + 2H2O(g) ∆H # = -520 kJ mol-1

6. Find the enthalpy change of the following reaction

C(s) + 2H2(g) CH4(g)

CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ∆H # = -890 kJ mol-1

)
H2(g) + ( O2(g) H2O(l) ∆H # = -286 kJ mol-1
C(s) + O2(g) CO2(g) ∆H # = -394 kJ mol-1

7. Using the given enthalpy values, determine the standard enthalpy of combustion of CH₃OH(g)
∆H!# CH3OH(g) = -238 kJ mol-1
∆H!# H2O(l) = -285.5 kJ mol-1
∆H!# CO2(g) = -393.5 kJ mol-1

8. C(s,graphite) + O2(g) CO2(g) ∆H # = -X kJ mol-1

2CO(g) + O2(g) 2CO2(g) ∆H # = -Y kJ mol-1

Determine the standard enthalpy of formation of CO(g)

3. Standard enthalpy change of bond dissociation

It is the enthalpy change when a gaseous compound in its standard state undergoes dissociation into
gaseous atoms or components in their standard states by breaking one mole of bonds

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 #
9. Find the ∆H$%& for the following reaction
CH3CH=CH2(g) + H2(g) CH3CH2CH3(g)

C=C C-C C-H H-H

∆H (kJ mol )
-1 614 347 413 432

#
10. Find the ∆H$%& for the following reaction
CH3CH2OH(g) CH2=CH2(g) + H2O(g)

C-O C=C H-O H-H C-H C-C

∆H (kJ mol )
-1 358 614 467 432 413 347

4. Standard enthalpy change of atomization

It is the enthalpy change when an element in its standard state is converted into one mole of gaseous
atoms in the standard state

5. Standard enthalpy change of sublimation

It is the enthalpy change when one mole of a solid element or one mole of a solid compound in its
standard state is completely converted into a gas in its standard state

6. Standard enthalpy change of fusion

It is the enthalpy change when one mole of a solid compound or element in its standard state is
converted into one mole of a liquid compound or element in its standard state

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7. Standard enthalpy change of evaporation

It is the enthalpy change when one mole of a liquid compound or element in its standard state is
converted into one mole of a gaseous compound or element in its standard state

8. Standard enthalpy change of solvation

It is the enthalpy change when one mole of gaseous ions in the standard state dissolves in a solution
to form a 1.0 mol dm⁻³ solution

9. Standard enthalpy change of hydration

It is the enthalpy change when one mole of gaseous ions in the standard state dissolves in water to
form a solution with a concentration of 1.0 mol dm⁻³

10. Standard enthalpy change of dissolution

It is the enthalpy change when one mole of a substance in its standard state dissolves in a solvent to
form a solution with a concentration of 1.0 mol dm⁻³.

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 11. Standard enthalpy change of neutralization

It is the enthalpy change when one mole of aqueous H⁺ ions and one mole of aqueous OH⁻ ions in
their standard states react to form one mole of liquid water.

11. A volume of 100.0 cm3 of 1.0 mol dm-3 HNO3 solution was mixed with 100.0 cm3 of 1.0 mol dm-3
KOH solution inside a heat insulated vessel. Assuming that the density and specific heat capacity of
the solution are equal to those of water, find the change in temperature of the solution
Standard enthalpy change of neutralization = - 57 kJ mol-1
Specific heat capacity of water = 4200 J kg-1 K-1
Density of water = 1 g cm-3

12. When 25.0 cm3 of 1.0 mol dm-3 KOH and 25.0 cm3 1.0 mol dm-3 HNO3 were mixed in a calorimeter,
the temperature was increased by 5 oC. What is the standard enthalpy change of neutralization of KOH
Specific heat capacity of water = 4.2 J g-1 oC-1
Density of water = 1 g cm-3

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 12. Standard enthalpy change of first ionization

It is the enthalpy change when one mole of gaseous monopositive ions in the standard state is formed
by removing an electron from each of the most weakly bonded atoms in one mole of gaseous atoms
of an element in its standard state

13. Standard enthalpy change of electron gaining

It is the enthalpy change when one mole of gaseous mononegative ions is formed by the gain of
electrons by one mole of gaseous atoms in the standard state

14. Standard enthalpy change of lattice dissociation of an ionic compound

It is the enthalpy change that occurs when one mole of a solid ionic compound is converted into its
gaseous positive and negative ions at standard state

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13. Draw a suitable thermochemical cycle and find the lattice enthalpy of NaCl(s)

Standard dissolution enthalpy of NaCl(s) = +1 kJ mol-1

Standard hydration enthalpy of Na+(g) = -406 kJ mol-1
Standard hydration enthalpy of Cl-(g) = -363 kJ mol-1

14. Using the following information find the standard enthalpy change of formation of ICl(g)

Standard sublimation enthalpy of iodine = 62 kJ mol-1

Standard bond dissociation enthalpy of I2 = 151 kJ mol-1
Standard bond dissociation enthalpy of Cl2 = 242 kJ mol-1
Standard bond dissociation enthalpy of ICl = 211 kJ mol-1

15. The following thermochemical data are given

Standard enthalpy of formation of KCl(s) = -437 kJ mol-1

Standard enthalpy of sublimation of K(s) = +89 kJ mol-1
Standard enthalpy of bond dissociation of Cl2(g) = +244 kJ mol-1
Standard enthalpy of first ionization of K(g) = +418 kJ mol-1
Standard electron gaining enthalpy of Cl(g) = -349 kJ mol-1

Calculate the lattice dissociation enthalpy of KCl(s)

Hess’s law

• If a process occurs in stages or steps, the overall enthalpy change is equal to the sum of the enthalpy
changes for each individual step

Born Haber cycle

• This primarily involves the lattice enthalpy and formation enthalpy of ionic compounds
• This is based on Hess’s law

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16. Find the lattice dissociation enthalpy of LiF(s) using a Born-Haber cycle

∆H!# LiF(s) = -594.1 kJ mol-1

#
∆H+,- Li(s) = 155.2 kJ mol-1
#
∆H./0 F(g) = 75.3 kJ mol-1
#
∆H12! Li(g) = 520 kJ mol-1
#
∆H23 F(g) = -328 kJ mol-1
#
∆H4 LiF(s) = ?

17. Using the provided data, calculate the formation enthalpy of ZnCl₂(s) by constructing a Born-Haber
cycle
The sublimation enthalpy of Zn(s) = 130 kJ mol-1
The 1st ionization enthalpy of Zn(g) = 906 kJ mol-1
nd
The 2 ionization enthalpy of Zn(g) = 1733 kJ mol-1
The bond dissociation enthalpy of Cl2(g) = 242 kJ mol-1
The electron gaining enthalpy of Cl(g) = -344 kJ mol-1
The lattice enthalpy of ZnCl2(g) = -2696 kJ mol-1

18. Draw a Born-Haber cycle and calculate the lattice enthalpy of MgCl2(s) using the data given below

∆H!# MgCl2(s) = -1080 kJ mol-1

∆H+# Mg(s) = +90 kJ mol-1
#
∆H1! Mg(g) = +180 kJ mol-1
∆H1#" Mg(g) = +208 kJ mol-1
∆H5# Cl2(g) = +320 kJ mol-1
#
∆H23 !
Cl(g) = -192 kJ mol-1

19. Using a Born-Haber cycle, determine the enthalpy change for the electron gain of chlorine

Standard enthalpy of sublimation of Ca(s) = 178.2 kJ mol-1

Standard enthalpy of first ionization of Ca(g) = 590 kJ mol-1
Standard enthalpy of second ionization of Ca(g) = 1145.0 kJ mol-1
Standard enthalpy of bond dissociation of Cl2(g) = 244 kJ mol-1
Standard enthalpy of formation of CaCl2(s) = -795 kJ mol-1
Standard lattice enthalpy of CaCl2(s) = -2253 kJ mol-1

Spontaneity of chemical reactions

• Thermodynamics tells us whether or not a reaction will occur, but it tells us nothing about the rate
• The release of heat by a reaction was once thought to be an indication of the spontaneity of reactions
• However, there are spontaneous reactions which are exothermic as well as endothermic
• Therefore, the sign of ∆H, by itself is not an adequate information to interpret about the spontaneity
of a reaction
• To interpret about the spontaneity of a reaction, in addition to the enthalpy another factor must be
considered
• …………………………………

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 Entropy

• It is a measure of disorder / randomness of a system

• It is a state function
• Units – J mol-1 K-1

Factors determining the entropy of a substance

Standard entropy change of a chemical reaction

Gibbs free energy (G) and the spontaneity of a reaction

• Gibbs free energy is a state function that combines enthalpy and entropy

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20. Calculate the standard free energy change for this reaction at 25 0C
)
CO(g) + ( O2(g) CO2(g)

∆H!# CO2(g) = -393.5 kJ mol-1

∆H!# CO(g) = -110.5 kJ mol-1
S # (CO2(g)) = 213.7 J mol-1K-1
S # (CO(g)) = 197.7 J mol-1K-1
S # (O2(g)) = 205.1 J mol-1K-1

21. At 25 0C, some standard data are provided for the reaction given below

CH4(g) + H2O(g) CO(g) + 3H2(g)

Standard entropy
Compound
J mol-1K-1
H2(g) 131
CH4(g) 186
H2O(g) 189
CO(g) 198

i. Calculate the standard entropy change (∆S # )

ii. If the enthalpy change of the reaction is 206 kJ mol-1, Calculate the standard Gibbs energy
change (∆G# )
iii. Hence predict the spontaneous nature of the reaction

22. In which of the following reactions will ∆S be positive

i. AgNO3(aq) + NaCl(aq) AgCl(s) + NaNO3(aq)

ii. H2O(g) + CO2(g) H2CO3(aq)
iii. H2(g) + I2(g) 2HI(g)
iv. H2O(g) H2O(l)
v. C2H2O2(l) 2CO(g) + H2(g)

23. The enthalpy change and entropy change for a particular decomposition reaction at 298 K are 51 kJ
mol⁻¹ and 118.74 J mol⁻¹ K⁻¹, respectively. At which temperature will this reaction become
spontaneous

24. For the reaction 2A + B C, ∆H # is +100 kJ mol-1 and ∆S # is 50 J mol-1 K-1. What is the
temperature at which this reaction will become spontaneous

25. Ice and water can exist in equilibrium at 0 °C and 1 atm pressure. At 0 °C, the entropy change that
occurs when 1 mole of ice is converted into water is 22 J mol⁻¹ K⁻¹. What is the enthalpy change that
occurs when 54 g of water is completely frozen into ice at the same temperature and pressure?

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