Chapter 5: Thermochemistry
• Thermochemistry is the study of the amount of heat involved in chemical reactions.
• The First Law of Thermodynamics
• system and surroundings
• work (w), heat (q), internal energy (E)
• Enthalpy H and enthalpy change DH
• DH = qp (constant P)
• path functions and state functions
• Enthalpy change DH measurement - calorimetry
• coffee-cup calorimetry and bomb calorimetry
• relating heat to mass/mole, heat capacity, temperature change
• calculations: qreaction + qwater/soln (+ qcontainer) = 0 (energy conservation)
• Enthalpy change DH calculations
• Hess’s law
• standard molar enthalpy
• molar bond enthalpy
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1. The First Law of Thermodynamics
a. System: the part of the universe under study
Surroundings: everything else that interacts with the system
b. Internal energy (E): is the sum of all the kinetic and potential
energies of the system
Two ways to transfer energy between system and surroundings:
heat (q) and work (w)
Example: Consider a cold pack, what is the system? the surroundings? is it an
exothermic or endothermic reaction?
𝑁𝐻! 𝑁𝑂" 𝑠 + 𝐻# 𝑂(𝑙) → 𝑁𝐻! $(𝑎𝑞) + 𝑁𝑂" % 𝑎𝑞 (𝑒𝑛𝑑𝑜𝑡ℎ𝑒𝑟𝑚𝑖𝑐)
System:
Surroundings:
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work w = FΔl = FΔh = -PΔV (force imbalance)
c. The First Law of Thermodynamics: Energy can be converted from one
form to another, but it is neither created nor destroyed.
The First Law: [Link] (11 min)
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2. Enthalpy H and enthalpy change DH
a. Enthalpy (H): a measure of heat content
b. Enthalpy change (ΔH): related to heat absorbed/released
H is a state function, independent of path, or ΔH = Hfinal - Hinitial (E is also a state function)
cold water hot water hot water low T water
low enthalpy high enthalpy high enthalpy low enthalpy
Heat and Enthalpy: [Link] (4 min)
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Reactants à Products
ΔH = Hfinal – Hinitial
ΔHrxn = Hproducts – Hreactants = qp
ΔH = qp (constant P) [ΔE = qv (constant V)]
i. ΔH can be measured by q when P is constant.
ii. Most processes occur at constant pressure!
Example: The heat required to vaporize 1 mol of water at 100 °C 100 and 1 atm is 40.7 kJ. What is ΔHrxn?
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3. Enthalpy change DH measurement - calorimetry
a. Coffee-cup and bomb calorimeters
calorimetry: [Link] (5 min) 6
b. Heat and heat capacities
SI unit for heat: J
other units for heat: 1 cal = 4.184 J; 1 Cal = 1000 cal
heat: q = c ΔT = n C ΔT = m csp ΔT where ΔT = Tfinal – Tinitial in K or °C
unit
heat capacity: 𝒄
molar heat capacity: 𝑪
specific heat capacity: 𝒄𝒔𝒑
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c. Calculations: heat/energy conservation!
- ΔT > 0
- ΔT < 0
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Practice problem: 100. mL of 0.50 M NaOH was mixed with 100. mL of 0.50 M HCl in a coffee cup
calorimeter. The temperature of the solution increased from 25.0 °C to 28.5 °C. What is the heat of the
neutralization reaction in kJ/mol? The specific heat for the solution is 4.18 J/(g °C) (same as water). The
density of water is 1.0 g/mL.
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Practice problem: 40. mL of cold water at 0 °C is added to a cup containing 400. mL of hot water at
98 °C. What is the final temperature after equilibration assuming there is no heat loss to the
surroundings?
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3. Enthalpy change DH calculations
a. Hess’s law: In going from a particular set of reactants to a particular set of products, the change in
enthalpy is the same whether the reaction takes place in one step or in a series of steps, i.e. treat chemical
equations as algebraic equations. This can be done because H is a state function.
Example: Let’s look at the enthalpy change associated with formation of CO (g) from C (s) and O2 (g).
!
𝐶 𝑠 + 𝑂" (𝑔) → 𝐶𝑂(𝑔) (1) ∆𝐻#$% (1) = ?
"
Given two related reactions:
𝐶 𝑠 + 𝑂" (𝑔) → 𝐶𝑂" (𝑔) (2) ∆𝐻#$% (2) = -393.5 kJ/mol
!
𝐶𝑂 𝑔 + 𝑂" (𝑔) → 𝐶𝑂" (𝑔) (3) ∆𝐻#$% (3) = -283.0 kJ/mol
"
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Steps:
1. Underline the reactants and products in the given equations
2. Determine sign and multiplication factor for each equation
3. Treat the corresponding equations and ΔH values accordingly
4. Add up all the manipulated equations and ΔH values
Hess’s Law: [Link] (14 min)
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Example: Diborane (B2H6) is a highly reactive boron hydride, which was once considered as a possible rocket fuel for the
US Space program. Calculate enthalpy change for the synthesis of diborane from its elements according to the equation
2𝐵 𝑠 + 3𝐻" (𝑔) → 𝐵" 𝐻& (𝑔)
using the following data: ΔH (kJ)
1. 2𝐵 𝑠 + 3/2𝑂" (𝑔) → 𝐵" 𝑂' (𝑠) -1273
2. 𝐵" 𝐻& 𝑔 + 3𝑂" 𝑔 → 𝐵" 𝑂' 𝑠 + 3𝐻" 𝑂(𝑔) -2035
3. 𝐻" 𝑔 + 1/2𝑂" 𝑔 → 𝐻" 𝑂 𝑙 -286
4. 𝐻" 𝑂(𝑙) → 𝐻" 𝑂(𝑔) 44
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b. Standard molar enthalpy of formation, ΔHfo : The change of enthalpy for the formation of one
mole of a molecule from its most stable constituent elements with all substances in their standard states
(1 atm, usually 25 °C).
Table 5.3 has ∆𝐻() values for many substances. ∆𝐻() = 0 for most elements; not C (diamond)
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-
Reactants → Products ∆H*+,
1. Reactants → elements − Σ∆H.- (reactants)
2. elements → products Σ∆H.- (products)
For a balanced reaction, aA + bB → yY + zZ
Practice Problem: Metabolism is the stepwise breakdown of the food we eat to provide energy for growth and
function. An overall equation for this complex process represents the oxidation of glucose (C6H12O6) to CO2 and H2O.
What is the standard enthalpy of the reaction at 298K using the standard molar enthalpy of formation data?
𝐶& H!" O& s + 6O" 𝑔 → 6CO" 𝑔 + 6H" 𝑂(𝑙)
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c. Molar bond enthalpy (gas phase)
2𝐻# g + 𝑂# g → 2𝐻# 𝑂 g
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Practice problem: Estimate ∆𝐻/01
)
for the following reaction using molar bond enthalpy information.
𝐶𝐶𝑙! g + 2𝐹# g → 𝐶𝐹! g + 2𝐶𝑙# g
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